Sustainable Recycling Technology For Li Ion

pubs.acs.
org/CR Review
Sustainable Recycling Technology for Li-Ion Batteries and Beyond:

Challenges and Future Prospects
Ersha Fan,∥ Li Li,∥ Zhenpo Wang, Jiao Lin, Yongxin Huang, Ying Yao, Renjie Chen,* and Feng Wu*
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ABSTRACT: Tremendous efforts are being made to develop electrode materials,

electrolytes, and separators for energy storage devices to meet the needs of emerging
Downloaded via UNIV OF GOTHENBURG on January 29, 2020 at 01:28:10 (UTC).
technologies such as electric vehicles, decarbonized electricity, and electrochemical energy

storage. However, the sustainability concerns of lithium-ion batteries (LIBs) and next-
generation rechargeable batteries have received little attention. Recycling plays an important
role in the overall sustainability of future batteries and is affected by battery attributes
including environmental hazards and the value of their constituent resources. Therefore,
recycling should be considered when developing battery systems. Herein, we provide a
systematic overview of rechargeable battery sustainability. With a particular focus on electric
vehicles, we analyze the market competitiveness of batteries in terms of economy,
environment, and policy. Considering the large volumes of batteries soon to be retired, we
comprehensively evaluate battery utilization and recycling from the perspectives of
economic feasibility, environmental impact, technology, and safety. Battery sustainability is
discussed with respect to life-cycle assessment and analyzed from the perspectives of
strategic resources and economic demand. Finally, we propose a 4H strategy for battery recycling with the aims of high efficiency,
high economic return, high environmental benefit, and high safety. New challenges and future prospects for battery sustainability are
also highlighted.
CONTENTS 5.3.3. Material Extraction Technology V

5.4. Current Industrial Recycling Process AB
1. Introduction B 5.5. Recycling of Next Generation Batteries AD
2. Evaluation of EVs D 6. Life Cycle Assessment of LIBs and Next Gener-
2.1. Economic Competitiveness of EVs E ation Batteries AD
2.2. Environmental Competitiveness of EVs F 6.1. Life Cycle Assessment of LIBs AD
2.3. Policy Incentives for EVs H 6.2. LCA of Next Generation Batteries AF
3. Failure Mechanisms of Batteries H 6.3. Resource and Economic Analysis AG
3.1. Batteries Progress H 7. Policy-Oriented Recycling Mode and Recovery
3.2. Failure Mechanisms J Status of Spent LIBs AH
4. Feasibility Analysis of LIB Ladder Based ESS L 7.1. Power Battery Ladder Utilization AH
4.1. Economic Indicators L 7.2. Valuable Metal Element Recycling AI
4.2. Technical Indicators M 7.2.1. US: Establishing a Sound Legal Frame-
4.3. Environmental Indicators N work for Battery Recycling AI
4.4. Security Indicators P 7.2.2. Germany: Building a Complete Power
4.4.1. Disassembly and Storage P Battery Recycling System AI
4.4.2. Screening and Reorganization P 7.2.3. Japan: The World’s Leader in Battery
4.4.3. ESS Utilization P Recycling Technology AI
4.5. Case Analysis P
5. Comprehensive Evaluation System for LIB Recy-
cling R
5.1. Environmental Impact and Energy Analysis R
5.2. Economic Analysis and Security Evaluation R Special Issue: Beyond Li Battery Chemistry
5.3. Technology Evaluation T Received: August 29, 2019
5.3.1. Pretreatment T
5.3.2. Crystal-Structure Repair Technology U
© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.chemrev.9b00535

A Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews pubs.acs.org/CR Review
Figure 1. (a) World primary energy demand from 2010 to 2040; percent share of primary energy by source in 2040 under the NPS (b) and the SDS
(c); (d) global CO2 emissions from 2010 to 2040. Adapted with permission from ref 3. Copyright 2019 International Energy Agency. (NPS:
Incorporates existing energy policies as well as an assessment of the results likely to stem from the implementation of announced policy intentions;
SDS: an integrated approach to achieving internationally agreed upon objectives on climate change, air quality, and universal access to modern energy.)
7.2.4. China: Introduction of Regulatory Docu- only account for 20% (Figure 1b).3 However, the use of fossil
ments and Improvement of the National fuels worldwide has released large amounts of carbon dioxide
Standard Recycling System AI and other greenhouse gases (GHG), which contribute to global
8. Conclusion and Future Perpectives AJ warming. In 2018, global CO2 emissions from fuel combustion
Author Information AK were 33.1 Gt CO2.4 To address the energy and environment
Corresponding Authors AK issues associated with nonrenewable fossil fuel combustion, a
Authors AK new approach to energy and sustainable development, namely
Author Contributions AK the sustainable development scenario (SDS), has been proposed
Notes AK to reduce energy-related CO2 emissions and develop renewable
Biographies AK energy sources (Figure 1c and 1d). In response, carbon-neutral
Acknowledgments AL electricity from renewable energy sources and electrification of
References AL the transportation sector are considered to be the most
promising solutions. Therefore, considerable efforts have been
made to develop advanced electrochemical energy storage
1. INTRODUCTION technologies and electric vehicles (EVs).
Rapid development of industry and increasing wealth of modern Lithium (Li)-ion batteries (LIBs) show great promise for
society highlight the great importance of developing a applications to electrical transportation and grid storage owing
sustainable and environmentally friendly economy.1 The to their high energy efficiency, high power density, and
world fossil fuel consumption in 2018 was 11,743.6 million environmental friendliness. Among electrochemical energy
tons of oil equivalent (Mtoe), accounting for 84.7% of the storage technologies, the cumulative installed capacity of LIBs
world’s energy consumption.2 Furthermore, fossil fuel combus- in 2018 accounted for the largest proportion, exceeding 86%
tion is expected to dominate the world’s energy consumption for (Figure 2a).5 In 2018, the global electric vehicle stock and newly
the near future (Figure 1a). It is projected that total world energy registered electric vehicles, including battery-electric vehicles
demand will increase to 17,651 Mtoe by 2040 under the IEA’s (BEVs) and plug-in hybrid electric vehicles (PHEVs), exceeded
New Policies Scenario (NPS), of which renewable energy will 5.12 million and 1.97 million, respectively, representing an
B https://dx.doi.org/10.1021/acs.chemrev.9b00535
Chem. Rev. XXXX, XXX, XXX−XXX
Figure 2. (a) Installed share of various electrochemical energy storage technologies in 2018. Data derived from ref 5. (b) Evolution of the global
electric car (EV and PHEV) stock and EV sales by country from 2010 to 2018. Adapted with permission from ref 6. Copyright 2019 International
Energy Agency. (c) Global EV stock in the EV30@30 scenarios from 2018 to 2030. Adapted with permission from ref 7. Copyright 2018 International
Energy Agency. (d) Lithium ion batteries demand by application and its market size forecast from 2019 to 2025. Data derived from ref 8.
expansion of 63% and 68%, compared with 2017.6 By 2018, price of Co in 2018 was $75991.27/t, which is more than five
more than 2.3 million electric vehicles will be on the road in and ten times as high as the prices of Ni and Mn,
China, accounting for approximately 45% of the world’s total, respectively.10,11 In addition, the average export price of
compared with approximately 24% for the European Union battery-grade Li2CO3 reached almost $12,514/t in March of
(EU) and 22% for United States of America (USA) (Figure 2019.12 The high content of metal in spent LIBs represents an
2b).6 By 2030, the forecast number of EVs on the road will reach important metal resource, especially because global reserves are
253 million under the EV30@30 Scenario (Figure 2c).7 As the limited to approximately 62 million tons of Li and 145 million
most popular technology for energy storage in applications tons of Co.13 Therefore, recycling of spent LIBs is highly
ranging from consumer electronics to EV and grids, it is worthwhile considering the need for sustainable use of these
predicted that the global lithium battery market demand in 2025 metals. Over the past decade, researchers have been committed
will reach $99.98 billion, and the shipment volume will be to developing high efficiency, low cost, and pollution-free spent
439.32 GWh (Figure 2d).8 Such huge LIB demand will result in LIB recycling processes. However, continuous development and
considerable consumption of resources for their manufacture. replacement of rechargeable batteries poses challenges to
Limited resources and strong demand for high energy recycling processes.
densities in EVs have motivated the development of next- The outline of this review is illustrated in Figure 3. As the main
generation rechargeable batteries to replace current LIBs. source of spent batteries in the future, the development of EVs is
Simultaneously, retiring of the current generation of EVs will crucial for the layout of retired batteries. Therefore, we first
create a need to recycle spent LIBs. It is predicted that by 2030 briefly analyze whether EVs represent an environmentally
the global LIB recycling market will reach $23.72 billion.9 friendly substitute for traditional fuel vehicles through a
Considering the need for effective use of these limited resources comprehensive environmental assessment and economic
and environmental sustainability, spent LIBs should be properly evaluation and consideration of policy support (Section 2).
handled and recycled. Spent LIBs contain heavy metal elements, The structure and failure mechanism of LIBs and new-
such as nickel (Ni) and cobalt (Co), which are classified as generation rechargeable batteries are introduced in section 3,
carcinogenic and mutagenic materials, as well as toxic organic conducive not only to design a battery structure that is easy to
electrolytes, which adversely affect human health and the disassemble and recycle but also to help recyclers safely, simply,
environment. As essential raw materials for synthesis of the and efficiently recycle batteries. Considering the large volumes
cathode materials of LIBs, Li and Co are in greater demand than of batteries soon to be retired, we comprehensively assess the
other metals because of their low relative abundance and high existing secondary use technology and recycling technologies for
price. According to the London Metal Exchange, the average retired power batteries from environmental, economic, and
C https://dx.doi.org/10.1021/acs.chemrev.9b00535
possibilities and difficulties of recycling rechargeable batteries

are considered (section 8), from which we discuss whether
rechargeable batteries are environmentally friendly, safe, and
sustainable and can form a closed loop from production to
recycling.
2. EVALUATION OF EVS
Intensification of urbanization has been driven by the rapid
growth of the social economy. Vehicle demand has also risen
dramatically, leading to a sharp rise in global oil consumption, oil
prices, and air pollution. Global oil demand was 99.2 million
barrels per day (mb/d) in 2018 and is set to increase by 5.5 mb/
d from 2018 to 2023 at an average of 1.2 mb/d a year.14
Following unprecedented expansion in 2018, oil production in
the USA has increased by a record 2.2 mb/d and will account for
70% of the increase in global production capacity until 2024,
Figure 3. Closed loop from production to recycling of LIBs and
ranking first in the world and adding a total of 4 mb/d.15
beyond. Fundamentally, oil demand depends on the strength of the
global economy. It is predicted that China and India will account
for 44% of the 7.1 mb/d growth in global demand by 2024.15
safety perspectives (sections 4 and 5). Guided by conventional Global oil reserves as of the end of 2018 are estimated to be
recycling processes for spent LIBs, the recycling technologies are 1,729.7 billion barrels and approximately, 48.3% of this oil is
proposed for future battery technologies. The sustainability of located in the Middle East.2 The crude oil price of Brent Spot of
LIBs and future battery technologies is analyzed through a 2018 reached 74 dollars per barrel ($/b), and it is predicted that
discussion of the life cycle assessment, strategic resource, and the crude oil price of Brent Spot will exceed 100 $/b by 2035.16
economic analysis (section 6). Next, we briefly examine the laws Global CO2 emissions from fuel combustion in 2017 were 32.79
and regulations of secondary battery use and recycling in the Gt CO2, of which oil combustion contributed 12.77 Gt CO2.17
USA, Germany, Japan, and China (section 7). Moreover, the Asia is the largest source of emissions, particularly China, which
Figure 4. (a) Comparisons of LCSCs and LCPCs. Reprinted with permission from ref 18. Copyright 2015 Elsevier. (b) Life cycle cost (LCC) of
internal combustion engine vehicle for different regions and life cycle cost of all-electric vehicle for different regions, both in thousand dollars.
Reprinted with permission from ref 19. Copyright 2015 Elsevier. (c) 10-year fuel costs for all EVs and ICEVs (€). Reprinted with permission from ref
21. Copyright 2018 Elsevier.
D https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 5. (a) EV electric demand from EVs by country, 2015−2018; (b) EVs stock and share by country, 2018. (c) GHG emissions avoided by EVs
compared to equivalent ICE fleet by mode and region, 2018. (a), (b), and (c) Adapted with permission from ref 6. Copyright 2019 International
Energy Agency. (d) Percent share of electricity generation by fuel (TWh) in China, EU, and US, 2018. Data derived from ref 2.
has reached 9.10 Gt CO2, followed by India at 2.08 Gt CO2.17 with activity over time, i.e., manufacturing, depreciation,
Transport was the main source of emissions in 2017, accounting operating and maintenance, insurance, and registration costs.
for 49% of the global total. Thus, energy security, high oil prices, The second category refers to the life-cycle social costs (LCSC),
and high CO2 emissions are a growing problem throughout the which are based on social or government positions and take into
world. account the social cost of CO2 and air pollutant emissions.
Increasing concerns about energy security, urban air The economic competitiveness of EVs in China has been
pollution, and high oil prices driven up by the transport sector analyzed in detail by Zhao et al.18 including the life-cycle private
have prompted global policy-makers and researchers to seek costs (LCPC) from the consumer perspective and LCSC from a
alternative fuels for transportation. EVs are considered to be one social perspective (Figure 4a). These economic analyses are
of the most promising alternatives to traditional internal based on the EV market and policies before 2015. Two different
combustion engine vehicles (ICEVs). Such vehicles are sized BEVs were selected from the Chinese EV market. They are
becoming capable of good energy efficiencies and reduced the compact vehicle shanghai-GM Sail Springo and the
carbon dioxide (CO2) emissions, and are sometimes termed multipurpose vehicle (MPV) BYD E6. They found that even
“zero-emission vehicles”. Three types of EVs have appeared on with central government subsidies, the LCPC for BEVs is
the current market, including PHEVs, hydrogen fuel-cell electric approximately 1.4 times as high as those of comparable ICEVs.
vehicles (HFCVs), and BEVs. It is unclear if EVs will become a The LCSC of EVs are also higher than ICEVs in the current
popular means of transport and replace ICEVs. Uptake will Chinese vehicle market. Therefore, from a social perspective,
depend on consumer purchase behavior and implementation of promotion of electric vehicles in China might not achieve the
policies and infrastructure in individual countries. The economic goal of reducing air pollution and greenhouse gas emissions in a
benefits of EVs influence the purchasing behavior of consumers, cost-effective manner. This is because the benefits of reducing
and the environmental benefits of EVs influence the degree of CO2 emissions from EVs do not offset the LCPC differences and
government implementation. The state of EV promotion also the government subsidies on EVs. However, owing to the great
affects consumers’ purchasing behavior. Therefore, we analyzed uncertainty of the social costs of pollutants and GHG emissions,
whether EVs as a replacement for ICEVs represent a more EVs might become socially more economically competitive.
environmentally friendly alternative and whether they save Tatari et al.19 investigated the life cycle cost (LCC) of five
energy. vehicle types in the USA, without considering battery
replacement costs. These results showed that for a variety of
2.1. Economic Competitiveness of EVs
reasons, such as changes in the future price of electricity, the
Economic competitiveness analyses of EVs, i.e., benefit-cost future electricity mix in the region, and future gasoline price, the
analyses, can be categorized into two types. The first considers life cycle costs of the studied vehicle types will change. The
the life cycle cost of ownership from a consumer standpoint, ICEV is the most cost-effective vehicle type with an average
including initial costs and likely future running costs associated LCC of $87,028, followed by BEVs, with an average LCC of
E https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 6. (a) Average well-to-wheels CO2 emissions for EVs and electric mixes in France, UK, and U.S. Reprinted with permission from ref 26.
Copyright 2010 Royal Society of Chemistry. (b) Life-cycle GHG emissions of vehicles per unit distance traveled (vehicle-cycle excluded). Reprinted
with permission from ref 23. Copyright 2018 Elsevier. (c) Fuel-cycle GHG emissions of gasoline ICEVs and EVs in the six regions, 2012 (1: China-
BTR; 2: China-YRD; 3: China-PRD; 4: U.S.-California; 5: U.S.-NPCC; and 6: U.S.-the three Midwestern states). Reprinted with permission from ref
27. Copyright 2015 Elsevier. (d) Potential WTW GHG reductions from BEVs. NE, NW, BJ, SH, CQ, and PRD represent northeast China, northwest
China, Beijing, Shanghai, Chongqing, and the PRD city group, respectively. Reprinted from ref 30. Copyright 2019 American Chemical Society.
$89,244. As shown in Figure 4b, the life cycle cost of an ICEV previous years, which is equivalent to 0.5% of total global
varies over a greater range and the uncertainty is also higher than electricity consumption.6 EV electricity demand in China and
that of BEVs. This uncertainty arises because of difficulty in Norway, which respectively have the largest fleet and the largest
predicting future gasoline prices versus electricity prices, and the market share of EVs (Figure 5b), account for less than 1% of
future electricity mix. Similar results have appeared in recent those countries’ total electricity demand.6 Therefore, current
research by Breetz et al.20 In almost all cities in the USA, the high EVs have a limited effect on electricity demand but will
purchase price of BEVs and their rapid depreciation far offset encourage greater electrical use. As the deployment of EVs
their potential fuel savings. increases, the effects of additional electricity demand on power
On the basis of the above analysis, there remains room for grids should be considered.
improving the competitiveness of EVs compared with ICEVs in 2.2. Environmental Competitiveness of EVs
most regions from a consumer standpoint. Many factors To address environmental and energy problems associated with
including government incentives, vehicle usage levels, battery ICEVs, some vehicles powered by alternative fuels have been
replacement, electricity mix, and fuel costs (oil and electricity proposed. These fuels include biodiesel, natural gas, methanol,
prices) might affect or change the economic competitiveness of ethanol, biomass fuel, and hydrogen, in addition to the
EVs. For example, O’Mahony et al.21 found that high levels of aforementioned hybrid and battery electric sources. EVs are
use and appropriate government incentives would make large considered to be the most promising of these alternatives.
EVs more economically competitive than ICEVs. Rises in However, several reports have questioned the ability of zero-
gasoline prices would also affect the fueling costs for ICEVs to a emission vehicles to address environmental problems associated
considerable extent, whereas a rise in electricity prices would with ICEVs. This is because although EVs have no direct CO2
only slightly affect fueling costs of EVs (Figure 4c). According to emissions during operation, they indirectly produce CO2
analysis by the IEA, the global electricity demand for all EVs in emissions, which are dependent on the country’s electricity
2018 is estimated to be 58 terawatt-hours (TWh), of which generation mix. Powering transport with electricity may transfer
China will account for 81% (Figure 5a).6 The estimated demand GHG emissions from distributed vehicle exhaust pipes to large
for EVs in 2018 increased by 17%, slightly less than in the two centralized power plants. The global use of EV in 2018 avoided
F https://dx.doi.org/10.1021/acs.chemrev.9b00535
Table 1. Related Policies of EVs in the Following Four Countries

Country Types Introduced Incentives
US Car subsidy 2008 The Energy Improvement and Extension Act and The United States Economic Recovery and Reinvestment Act have granted
federal tax credits to newly registered EVs and modified EVs since 2008. The federal tax credit for the purchase of
EVs is $2500 plus the vehicle battery capacity of $417 per unit, up to $7500
Infrastructure subsidy 2018 California’s Executive Order B-48-18 includes a proposal to invest USD 900 million to deploy 250 000 charging points
by 2025, of which around 10 000 outlets should be DC fast chargers
traffic pass 2005 In California, electric cars are given High-Occupancy Vehicle Lanes.
R&D and 2008 ARRA provide $2.4 billion to EVs sector, of which $2 billion is used to support the construction of the EVs supporting
industrialization industrial chain.
Local policy 1990 California’s Zero Emission Vehicle (ZEV) policy forces auto companies to promote zero-emission vehicles by
stipulating a combination of zero-emission vehicle sales and autotransactions.
2016/2018 California’s governor issued an executive order to call for 1.5 million ZEVs on the road by 2025/Add a new executive
order to achieve the goal of 5 million ZEVs in California by 2030.
Energy conservation 2018 EPA announced a change in the GHG emissions standards for new light-duty vehicles sold between 2022 and 2025.
and environmental This standard is a regulatory requirement of the 2012 rule establishing the GHG emission standards for the
protection policy 2017−2025 period.
Japan Car subsidy 2009 Providing car subsidies for cars that meet the corresponding environmental requirements. The subsidy amount is 50%
to 100% of the difference between the clean energy vehicle and the prototype vehicle.
Green Vehicle Purchase Promotion Measures provide tax reduction or exemption for the environmentally friendly and
energy efficient vehicles and increase the tax rate for the high environmental load and high fuel consumption vehicles.
Infrastructure subsidy 2013 Since 2013, 2/3 of the total amount of charger purchase and installation engineering fees, ranging from 200,000 yen to
3.33 million yen.
R&D and 2018 Reduction of 80% of GHG emissions per vehicle produced by Japanese automakers by 2050.
industrialization
traffic pass 2015 Short-term implementation of highway toll subsidies from May 2015 to March 2016
Local policy 2009 Proposed “Pure Electric Vehicle/Hybrid Electric Vehicle (BEV/PHEV) City” initiative in 2009.
Norway Car subsidy 1990/1996 Exemption from registration tax
2001 VAT with 25% discount
1996/2004 Reduced annual vehicle license fee
2000 Reduced imposed taxable benefit on company cars
Infrastructure subsidy 2009/2011 Financial support for charging stations/Fast charge stations
traffic pass 1997/2003/1999 Free toll roads/Access to bus lanes/Free parking
China Car subsidy 2009 Direct car purchase subsidy. Car purchase subsidy is lowered year by year.
2014−2017 Exemption from vehicle purchase tax
2012 Exemption from vehicle and vessel tax
Infrastructure subsidy 2016−2020 Awarded RMB 30 million to RMB 200 million for the construction and operation of charging facilities in various
provinces
R&D and 2016 The 13th Five-Year National Science and Technology Innovation Plan
industrialization 2017 National key research and development plan, new energy vehicles and other key special projects 2017, 2018 annual project
application guide. Provide RMB 1.12 billion in 2017 and RMB 900 million in 2018 to develop EVs
2018 New energy vehicle (NEV) credit mandate requires OEMs to produce a minimum share of NEV cars.
Energy conservation 2017 “The average f uel consumption of passenger car business with the parallel integration of new energy vehicles management
and environmental approach”
protection policy 2019 “Energy consumption rate limits for electric vehicles”
traffic pass 2017 There is no need to shake the number in the restricted area; the restricted area is no longer affected by the license
number. Free parking for 2 h in some public parking lots or halved parking fees
Local policy 2014 Beijing: The new energy vehicle is licensed to implement independent allocation indicators. New energy vehicles are
not subject to restrictions
about 40 Mt CO2-eq emissions, with China contributing the majority (66.5%) of China’s power generation in 2018, followed
most (Figure 5c).6 However, this result reflects the large by hydroelectricity (16.9%) and renewable energy sources
magnitude of the EV stock in China, rather than a significant (8.9%). In the USA, coal-fired and natural gas-fired power plants
advantage of EVs over ICEVs in terms of CO2 emissions given dominate the electricity generation mix, accounting for 27.9%
the high carbon intensity of China’s power generation mix. and 35.4%, respectively, in 2018. Therefore, for countries that
Therefore, the ability to reduce CO2 emissions by EVs depends rely primarily on coal for electricity production, the environ-
on the fuel mix used to generate the electricity that drives EVs. mental effects of EVs and ICEVs should be analyzed and
Among all power generation technologies, coal continues to compared in depth over their life cycles.
account for the majority of the world’s power generation, with a The environmental effects of EVs in different countries with
share of 38% in 2018, which is almost as great as the second and different electricity generation mixes have been previously
third largest contributions combined, namely natural gas studied.22−25 For example, in 2010, Holdway et al.26 analyzed
(23.2%) and hydroelectricity (15.7%).2 The share of power indirect well-to-wheels CO2 emissions from EVs run in the USA,
generation from renewables was 9.3% in 2018, having risen 6.3% United Kingdom (UK), and France and compared these
percentage points since 2008.2 At the end of 2018, the emission data with results for a selection of ICEVs and HEVs.
recoverable reserves of coal in the USA and China were 250.2 The well-to-wheels CO2 emissions for the EVs were calculated
billion tons and 138.8 billion tons, respectively, accounting for based on well-to-power-plant emissions and power-plant-to-
23.7% and 13.2% of the world’s total.2 As shown in Figure 5d, in wheels emissions. The electricity grids of these three
China, coal-fired electricity generation accounted for the industrialized countries are fed by different mixes of renewable
G https://dx.doi.org/10.1021/acs.chemrev.9b00535
and fossil fuel sources: in the USA, coal power dominates; in the the mix, BEVs have lower emissions than ICEVs in 2012,
UK, the share of natural gas is equal to coal; and in France, meeting the government’s MY2020 NEV target. In consid-
nuclear energy accounts for the largest share (78%) of power eration of the high proportion of coal-fired electricity produced
generation. The amount of CO2 emissions from EVs in the US is in China today, BEVs are not a favorable option for meeting
slightly higher than from those in the UK, whereas CO2 GHG reduction commitments in all regions (Figure 6d).30
emissions from EVs in France are much lower than those in Seeking cleaner energy to power EVs is the key to the long-term
either of the other countries (Figure 6a). This is because CO2 GHG reduction.
emissions from the nuclear power-heavy electricity mix in 2.3. Policy Incentives for EVs
France are less than half the average of those from coal, oil, and
Sales of EVs remain far below those of traditional vehicles;
natural gas sources.26 Therefore, to achieve greater reductions of
however, the number of EVs has increased rapidly since 2010
CO2 emissions, electricity grids must be decarbonized,
and the global EV fleet exceeded 5 million in 2018.6 In the USA,
particularly when comparing EVs and ICEVs. Thus, decarbon-
Japan, Norway, and China, fast-growing sales of EVs have mostly
ization of electricity production should be synchronized with the
been driven by implementation of related government policies.
development of EVs.
As shown in Table 1, these incentives policies can be categorized
Taking into account changes in the power grid mix in China,
into the following types: car subsidies, infrastructure subsidies,
the USA, Japan, Canada, and the EU, Ou and co-workers23 traffic passes, research and development and industrialization
developed a scalable EV life cycle assessment (LCA) model to policies, energy saving and environmental protection policies,
analyze the life cycle energy consumption and GHG emissions and local policies.6,7,31 Government policies tend to be biased in
of EVs. The system boundary of an LCA of a vehicle-fuel favor of EVs compared with other vehicle types. The USA EV
combination usually includes both the fuel cycle and the vehicle industry support policy is relatively comprehensive and
cycle (materials production and transportation, vehicle implements subsidies from the state to local level, covering
manufacture, decommissioning, and recycling). As shown in vehicles and charging facilities. The focus is to encourage
Figure 6b, current BEVs show a positive performance in GHG consumers to purchase and cultivate market factors, thereby
emissions reduction (ranging from 30%−80%) compared with promoting the development of EVs. Japan has focused on the
ICEVs. Huo and co-workers27 conducted an LCA of EVs in development of key technologies for EVs and supports an
China and the USA, based on their electricity mixes in 2012. As alliance of companies to jointly develop core technologies and
shown in Figure 6c, in those regions with a low share of coal- enhance the market. Norway is the first country to implement a
based electricity (e.g., California), EVs markedly reduced GHG subsidy policy for EVs and because of large subsidies, has the
and air pollutant emissions (except for PM) compared with world’s highest share of EVs in its vehicle stock at 46.4% in
conventional vehicles. However, in regions of China and 2018.6,31 In addition to supportive policies, China has
selected USA Midwestern states where coal dominates the introduced a planning policy and new energy vehicle
electricity generation mix, EVs reduced GHG emissions but demonstration and promotion policies to support and guide
increased total and urban emissions of air pollutants. It is the rapid development of the EV industry. China’s policy has
predicted that if EVs are charged with 80% renewable electricity, shifted from financial subsidies to a points system and from the
GHG emissions might be reduced by more than 85%, SO2 and demand to the supply side. However, for the Chinese market,
NOx emissions reduced by more than 75%, and PM emissions EVs remain more expensive than ICEVs. Therefore, the Chinese
reduced by more than 40%. Therefore, the life cycle emissions of government should further support technological improvements
EVs depend on the carbon intensity and the cleanness of the to reduce the high initial cost of EVs.
electricity grid mix. On the basis of the above analysis, we conclude that more
Owing to the high proportion of coal-fired electricity in comprehensive policies are essential to lay foundations for a
China, Zhang et al.28 found that the life cycle GHG emissions of transition to electrification. The level of car subsidy allocated
EVs with and without the use of CO2 capture and storage (CCS) depends on four characteristics: the vehicle range in kilometers
technology can be reduced by 3%−36% and 60%−70% (km), energy efficiency in kilowatt-hour per 100 km (kwh/100
compared with those of ICEVs. However, direct use of coal km), battery pack energy density in Watt-hour per kilogram
rather than petroleum as a fuel for the transport sector must be (Wh/kg), and CO2 emissions in g/km. These car subsidy
considered. Although coal can save energy (particularly when policies are intended to push original vehicle manufacturers to
compared with petroleum), it increases GHG emissions because invest in manufacture of EVs. The focus on battery performance
it is a high-carbon content fuel. Wang et al. and co-workers drives car makers toward battery chemistries with higher energy
conducted an LCA to compare energy consumption and CO2 densities. Increasingly stringent regulations on reducing tailpipe
emissions of three types of vehicles, including ICEVs, EVs, and CO2 emissions have also prompted automakers to manufacture
FCVs (fuel cell vehicles).29 On the basis of Chinese electricity and sell zero-emission or low-emission vehicles. Policy-makers
grids in 2009, EVs and FCVs based on water-electrolyzed also need to set appropriate policies for charging infrastructure
hydrogen power might contribute to more serious energy and and grid services to achieve viable business models and facilitate
environmental issues. Because they would be less dependent on smooth integration of EVs into power grid operations.
the Chinese electricity mix, FCVs based on hydrogen from
natural gas reforming might reduce pollutant emissions and 3. FAILURE MECHANISMS OF BATTERIES
result in energy conservation. In addition, Shen et al.24
specifically analyzed several cities in China. The GHG emissions 3.1. Batteries Progress
of EVs in selected regions and cities are different. In the North Increasing demand for sustainable energy has driven techno-
and Northwest regions and Beijing, BEVs have lower emissions logical improvements in rechargeable batteries. Nearly 30 years
than ICEVs, but do not meet the government’s MY2015 NEV after commercialization, LIBs have become the primary choice
target. In the Central and Southern regions and Guangzhou, for energy conversion and storage in portable electronic devices,
where renewable and nuclear power account for 36%−38% of hybrid electric vehicles, and off-peak energy storage. As LIBs
H https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 7. (a) Radar maps of the LIBs based on different cathode materials. (b) Market share in 2016 and 2025 of five types of LIBs. Reproduced with
permission from ref 36. Copyright 2018 Wiley.
Figure 8. (a) Voltage versus capacity for positive- and negative-electrode materials presently used or under serious considerations for the next
generation of rechargeable Li-based cells. Reprinted with permission from ref 38. Copyright 2001 Springer Nature. (b) Average voltage and energy
density versus gravimetric capacity for selected positive electrode materials for NIBs. Reprinted from ref 39. Copyright 2014 American Chemical
Society. (c) Capacity versus voltage plots of electrode materials for KIBs. Reprinted with permission from ref 43. Copyright 2017 Wiley. (d) Capacity
versus voltage for the reported electrode materials for secondary magnesium batteries. Reprinted with permission from ref 34. Copyright 2016 Wiley.
become more extensively used, researchers have conducted in- are widely expected to take on a role as next-generation batteries
depth research on electrodes to identify electrode materials with to replace LIBs. These predictions are based on Li metal
high energy densities, high safety, and low cost. However, even batteries having specific energy capacities higher than 500 Wh
state-of-the-art LIBs that achieve their theoretical energy storage kg−1 through the use of a high-capacity cathode, such as high-
capacities will not meet demands and challenges of current nickel-content lithium nickel manganese cobalt oxide, with S,
energy storage and power applications (particularly EVs).32 and O2.32 However, the uneven distribution and limited nature
Owing to its high energy density, Li metal is considered to be the of Li resources have prompted researchers to develop alternative
ultimate anode material.33 Therefore, Li metal batteries (LMBs) advanced rechargeable batteries to ease the burden of resources
I https://dx.doi.org/10.1021/acs.chemrev.9b00535
and costs. These include Na-, K-, Mg-, and aluminum (Al)-based On the basis of the lower price and abundant reserves of
battery technologies. Rechargeable batteries based on these sodium salts, sodium-ion batteries (NIBs) represent potential
metals have similar structures and energy storage mechanisms, alternatives to LIBs.39 Research on Na+ as a charge carrier for
which involve charge transfer within the electrode materials. On electrochemical energy storage began in the 1980s. Early
the basis of their operating principle, all rechargeable batteries research focused on electrode materials for Na+ intercalation
can be categorized as follows. The first group involves batteries reactions, such as MoS2, TiS2, and NaxCoO2.40,41 However,
consisting of intercalation-compounds based on monovalent intense research into LIBs was prompted by Sony’s first
charge carriers (i.e., Li+, Na+, and K+) and multivalent cations commercialization of LIBs in 1990, whereas NIBs research
(Mg2+ and Al3+), in which the relevant cations move from the stagnated over the following 20 years. In the time since, several
cathode to the anode during charging and vice versa during leaps in development, including the use of hard carbon in a Na
discharging.34 The second category is Li metal batteries, such as cell by Stevens and Dahn in 200042 and the application of a
Li−O2 and Li−S batteries, in which anions also take part in Fe3+/Fe4+ redox couple, have renewed interest in NIBs. The
conversion reactions.35 estimated energy densities of NIBs combined with develop-
Current commercial LIBs can be categorized into five types: ments in positive electrode materials and hard carbon as a
LiCoO2 (LCO) series, LiNixCoyMnzO2 (NCM, x + y + z = 1) negative electrode have exceeded 300 mWh g−1, which is
series, LiNixCoyAlzO2 (NCA, x + y + z = 1) series, LiMn2O4 competitive with graphite/LiMn2O4 systems (Figure 8b).39
(LMO) series, and LiFePO4 (LFP) series. A comparative Here, the estimated energy density was calculated with the
analysis of their electrochemical performances in terms of cycle assumption of 300 mAh g−1 for hard carbon as a negative
life, cost, safety, energy density, and voltage platform is electrode material as full cells. Simultaneously, high global
illustrated in Figure 7a. All types of LIBs have advantages and demand for EVs and ESS and Li resource shortages have
limitations. Because of their high voltages, LCO batteries were motivated research into NIBs and KIBs. Owing to the large
the earliest developed Li-ion battery in the 1990s and are widely radius of K+, the energy density of KIBs is less than that of LIBs,
used in consumer electronics products. The LFP and LMO which has hindered the application of KIBs with K+ as carriers.
batteries are superior to LCO in terms of cost and safety. At present, common cathode materials for KIBs are layered
Compared with other battery types, NCM and NCA batteries materials, metal−organic frameworks, polyanionic compounds,
have advantages in terms of their energy density. However, and organic materials. The negative electrodes are graphite
demanding production processes have limited the development materials and composite materials based on alloying reactions
of NCA batteries and the low energy density and high (Figure 8c).43 The hazard posed by the high reactivity of K is
temperature performance of LMO batteries have led to its low one reason why KIBs have yet to be practically applied.
market share (Figure 7b).36 Therefore, LFP and NCM batteries Multivalent rechargeable batteries with polyvalent ions exhibit
currently dominate the market. Owing to their low cost, high potential for a capacity several times higher than that of current
safety, and long cycle lives, LFP batteries are mainly used in EVs LIBs, such as magnesium ion batteries and Al-ion batteries. The
and electrical storage system (ESS). NCM batteries are also first magnesium-ion batteries were assembled by Gregory et al.44
widely used in EVs because of their high energy density. Because in 1990. A key breakthrough in electrolytes and cathode
of their high weight percentage and production cost, the cathode materials was made by Aurbach et al.,45 who in 2000 obtained
has a high recovery value and a high degree of concern for magnesium-ion batteries with a high capacity and good cycling
recovery.37 The cost of the graphite anode is lower than that of and safety performance. Although magnesium metal anodes are
the cathode but also accounts for a high weight percentage of not affected by dendrite formation, oxidation and polarization of
Mg2+ are the main obstacles affecting the development of
LIBs. In addition, the anode may contain large amounts of
magnesium batteries.46 Solving these problems is the current
residual Li after charging and discharging. Thus, researchers
direction of research into magnesium batteries. Studies of Mg2+
have also focused on anode recycling. However, other
intercalation hosts materials have included Chevrel phases,
components of LIBs, including steel, plastics, the separator,
transition metal-oxides, sulfides, borides, olivine-type polyanion
and electrolyte, also require treatment and recycling owing to
compounds, Prussian blue analogs, and organic materials
their high recovery value and potential for environmental
(Figure 8d).34 Because Al has a low atomic weight and a high
pollution. Spent LIBs pose potential dangers from residual
density, its capacity as a battery anode is expected to be twice
electrical charge, toxic organic electrolytes, and hazardous heavy
that of a magnesium-based anode.46 Al was first used as an anode
metal elements. Therefore, from both economic and environ- in the Buff cell in 1857 and in an Al-air battery anode in 1962.47
mental perspectives, recycling of spent LIBs is worthwhile. Since the 1970s, researchers have focused on nonaqueous
As the optimal electrode material, metallic Li has an ultrahigh electrolyte battery systems, particularly molten salt battery
capacity (3680 mAh g−1) and low negative electrochemical systems. In 2015, Dai et al. reported an Al-ion battery and
potential (−3.040 V vs the standard hydrogen electrode). proposed a complete reaction mechanism, based on Al as an
Hence, LMBs are predicted to take over as next-generation anode in combination with a graphitized foamed carbon cathode
batteries (Figure 8a).38 The theoretical energy densities of Li− and an ionic liquid as the electrolyte.48 Since this development,
O2 and Li−S are 3505 and 2600 Wh kg−1, respectively, and research interest in Al-ion batteries has grown.
much higher than that of current LIBs. However, uncontrollable
Li dendrite growth induces low cycle efficiency and introduces 3.2. Failure Mechanisms
serious safety problems, which has delayed practical application The rapid proliferation of spent batteries places a considerable
of Li metal batteries.35 Various methods have been explored to burden on recyclers, not only because of their limited service life
suppress Li dendrite growth, such as electrolyte modification, Li but also because of other factors, such as battery expansion, short
surface protective layers, and matrix design; however, the exact circuiting, performance degradation, and electrolyte leakage.49
operating and failure mechanisms for Li metal anodes continue Therefore, understanding the failure mechanisms of LIBs and
to elude researchers. next-generation rechargeable batteries is also beneficial for their
J https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 9. Schematic diagram of four aspects in existing degradation mechanisms for rechargeable batteries.
safe and efficient recovery. From the perspective of battery controlled Li/electrolyte interface.50 Porous cathode clogging
structure, the main causes of failure in rechargeable batteries can caused by discharge product Li2O2 and byproducts is the main
be analyzed from the following four aspects: cathode reason for the failure of the cathode of Li−O2 batteries.50 In
restrictions, anode restrictions, electrolyte restrictions, and addition, the formation of Li dendrites is a critical issue for Li
separator restrictions. A schematic diagram outlining these metal anode, causing several fatal obstacles, including cell short
degradation mechanisms is illustrated in Figure 9. circuit, aggravated adverse reactions, evolution of dead Li from
The cathode and anode failure for metal ion batteries can be dendrites, increased polarization, and large volume change.35
categorized into the following: the structural failure and particle In general, capacity fading of electrode material can originate
cracking of the electrode materials; corrosion of the current from two basic principles: structural changes during cycling and
collector and binder decomposition; the dissolution of chemical decomposition/dissolution reaction. Therefore, a
transition metal in the cathode material; overgrowth of the suitable recovery method can be selected to maximize recovery
solid electrolyte interphase (SEI) on the anode surface, resulting of electrode materials, with particular focus on cathode
in a lack of Li in the batteries internal system; accumulation of materials. For the not damaged electrode materials and other
dendrites at the anode, causing short-circuiting or explosion components, the researchers used the simple physical separation
during overcharging and over discharge processes. All the or direct recycling to recover these materials. Repair and direct
scrapped rechargeable batteries may have decomposition and regeneration by adding metal ions and heat-treating the material
deterioration of the electrolyte, as well as the aging, puncture, can be used to recover the failure cathode material caused by the
and clogging of the separator. Li−S batteries have several lack of metal ions, repairing the electrochemical properties of
inherent problems, including (1) the insoluble Li2S2 or Li2S can cathode materials. Batteries that have failed through severe
deposit on the anode; (2) the generation of various soluble damage to the cathode materials can be recycled by material
polysulfide Li2Sn (3 ≤ n ≤ 6) intermediates; (3) poorly extraction technologies, such as hydrometallurgy and pyrome-
K https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 10. (a) Home energy storage appliance cost estimates of three vehicles. Reproduced with permission from ref 54. This report was prepared for
California Energy Commission by University of California and approved for public release; further dissemination unlimited. (b) Breakout of capital,
labor, and total annual costs for the baseline scenario where the repurposed battery selling prices are $180/kWh and $44/kWh, respectively.
Reproduced with permission from ref 56. This report is available at no cost from the National Renewable Energy Laboratory at www.nrel.gov/
publications. (c) Cost breakdowns for high and low values of the substation on-site power application with 4.4 kW peak power and 26.4 kWh storage
capacity; (d) Cost breakdowns for high and low values of the electric service power quality application for residential users with 1 kW peak power and
0.0083 kWh storage capacity. (c and d) Reproduced with permission from ref 52. This report is generally available free via the U.S. Department of
Energy Information (http://www.osti.gov/contact.html).
tallurgy. These same principles apply to recovery of anode from economic, technological, environmental, and safety
materials. The recycling method will be discussed in detail in perspectives.
section 5. 4.1. Economic Indicators
Economic feasibility analyses are important for assessing
4. FEASIBILITY ANALYSIS OF LIB LADDER BASED ESS industry acceptance of projects. Three economic issues raise
Given a typical 5−8 year service life of LIBs in an EV, many LIBs questions: whether it is profitable to reuse retired EV batteries
will start to enter retirement in 2019. The volume of retired LIBs for certain secondary applications; whether there is sufficient
will increase together with production and promotion of EVs as market for secondary batteries; and whether it is worthwhile to
a green transportation choice; hence, an exponential increase in retire EV batteries prematurely to improve the profitability of
retried LIBs is expected by 2050.37 EV manufacturers specify their secondary applications.
that a battery is unsuitable for continued use in a car when the Cost−benefit analyses are essential to evaluate the economic
energy or power density drops to 70%−80% of its original value. profitability of secondary use of retired EV batteries. The cost of
The large volume of retired LIBs and low accessibility to raw the repurposing EV batteries should consider the following two
materials for LIB production threaten production sustainability types of cost: the repurposing cost, including the cost of retired
and raise environment concerns. Two approaches have been EV batteries; transportation costs, logistics, testing, and
refurbishment costs, and the cost of energy storage applications
proposed to deal with the retired EV batteries: energy storage
as determined by the repurposing cost, operation and
system (ESS) utilization and disassembly to recover the active maintenance cost, and the balance-of-system costs.51−53 For
constituents. The method selected mainly depends on the example, Williams et al.54 calculated the cost for reuse of retired
performance and condition of the retired batteries and the cost EV batteries from three actual vehicles, namely the Toyota Prius,
and benefits of the chosen method. Because retired EV batteries Chevrolet Volt, and Nissan Leaf, which have consistent residual
contain a substantial electrical charge capacity, secondary capacities (Figure 10a). Among energy storage application costs,
utilization is considered to be a promising solution to reuse the cost of power conditioning, controls, and interfaces, which
remaining capacity and extract additional value from retired EV are the balance-of-system costs, were the major components in
batteries. In addition, secondary use alleviates the need for large- all cases (54%−58%). The repurposing cost only accounted for
scale scrapping of power batteries and relieves pressure on the 6%−8% of the total cost. The cost calculation is based on an
upfront costs of electric vehicles. Therefore, we comprehen- upfront battery cost of 825 $/kWh in 2010 and a cost of 100
sively examine the feasibility of secondary use of retired batteries $/kWh plus $1000, which is added to capture the minimal
L https://dx.doi.org/10.1021/acs.chemrev.9b00535
battery management system (BMS) costs. The market price for a Hence, modules are directly characterized in the form of basic
secondary battery ESS would range from $1875 to 2030/kWh units, and then integrated into ESSs without disassembly. This
and $111 to 248/kWh for a battery pack alone. Additionally, the approach takes advantage of the various components of the
maximum allowable repurposing cost was considered to be the module and reduced integration costs. Thus, this technical route
new battery costs. has gradually been adopted. First, detection and classification are
Although market prices for second-use batteries have been necessary before ESS utilization, which are usually performed by
estimated, some uncertainty remains. To improve the accuracy evaluating the external and internal characteristics of the retired
of such predictions, Neubauer et al.55 constructed a complete batteries, through an observational check, battery capacity
framework to estimate the selling price of second-use batteries, measurements, pulse characteristic curves, and electrochemical
considering the battery salvage value of the retired batteries. impedance spectroscopy.59 However, Liao et al.60 found that
They estimated that the repurposed battery selling price would
these observational checks and capacity measurements are only
range from $38 to $132 kW h−1 based on a retired battery price
a preliminary way of screening and classifying retired batteries.
of $20−$100/kWh. They also found that module size and cell
fault rate can strongly influence the repurposing cost. The The voltage of pulse discharge is an important indicator for
optimal module size decreased as the cell fault rate increased and evaluating the consistency of retired batteries. There is no
smaller modules were more economically favorable than larger correlation between capacity loss and ohmic resistance.
ones. Therefore, it is not recommended to replace faulty cells for However, there are still some key technologies that need to be
economic considerations. When a retired EV battery is used in developed, related to evaluating the performance of retired
an uninterruptable power system, a return on investment period batteries. Key areas include testing of retired batteries state-of-
of less than 7 years can be achieved, which is more cost-effective health (SOH), prediction of second-use performance, battery
than existing lead acid technologies. In a recent study, based on sorting and clustering, battery reorganization, energy storage
new battery prices in the range of $150 and $250/kWh, the system integration, and practical applications.56,60−63
refurbishment cost of second-use batteries was predicted to Among battery health assessment techniques, the most
range from $25 to $49/kWh.56 Figure 10b shows a breakdown of challenging technologies are key to turning the concept of
the costs of a repurposing facility for both the lowest ($44/kWh) ESSs into industrial reality because of the unknown battery
and highest ($180/kWh) calculated repurposed battery selling performance after decommissioning. The reliability of technical
prices. The retired battery purchases dominated the total system or economic feasibility analyses is highly dependent on the
cost (45% and 76%), followed by labor costs (39% and 9%). The battery degradation behavior. The remaining capacity and
cost of technicians accounts for 60% of the total labor costs, power capability of retired batteries can currently be determined
representing a key area for cost reduction. by specific testing procedures, such as “Technical specifications
However, it remains unclear if the main cost consumption is of performance test for smart grid energy storage batteries”
the repurposing cost or the energy storage application cost. (DB31/T817-2014, China) and “USABC Reference Perform-
Narula et al.52 addressed this problem and found that when ance Test”.51,60 The National Renewable Energy Laboratory
retired batteries are used in high energy capacity demand
under the support of the U.S. Department of Energy’s Vehicle
scenarios, the retired battery costs and the cost of transportation
Technologies Office have developed a methodology and tools to
dominate the overall system cost (Figure 10c). When applied to
high-power demand scenarios, the main costs are the balance of predict battery degradation during primary and secondary use,
the system cost and the operation and maintenance cost (Figure including the Battery Lifetime Simulation Tool (BLAST).
10d). On the basis of the above analysis, we note that the cost of Neubauer et al.63 introduced these methods and tools to verify
using retired batteries in ESS is lower than the cost of new their application. They found that if managed properly,
battery applications. In addition, improvements in related repurposed automotive batteries can last 10 years or more in a
technologies, such as refurbishment, operation and main- second use under a presumed secondary use duty cycle of daily
tenance, and balance-of-system, are key to reducing the overall peak shaving. Compared with resistance growth, capacity fading
cost. from primary EV use has a considerable effect on the secondary
4.2. Technical Indicators use value. Driver patterns and climate are the main factors that
affect battery degradation.
Technical routes applied to reuse of retired batteries, can be In addition, Ahmadi et al.61 considered a simulated capacity
mainly divided into two types: the residual value of the retired fading model dependent on constant temperature, C-rate, DOD,
battery cells or battery modules. The former refers to and state-of-charge (SOC) for the EV LIBs with a limited
disassembling the decommissioned battery module first, testing number of charge/discharge cycles. A degradation curve
the disassembled battery cells, and restoring according to battery
consisting of an initial exponential trend and subsequent linear
capacity, internal resistance, and other external characteristic
degradation occurs during the first life aging, and a slower linear
parameters. The battery is then reorganized and a new electric
heating and safety management system is installed to form a degradation is found in the second lifetime. In a similar manner,
battery module. Finally, the implementation of ESS integration Wieland et al.64 considered a slower second life aging, which
is based on the reconstituted battery modules. Owing to the benefits from a milder C-rate and temperature operating
large difference in performance of decommissioned single cells conditions. In contrast, a faster aging trend in the second life
and the uneven remaining capacity, the technical route for of the battery has been proposed by Debnath et al.65 and Sathre
disassembly of modules is generally used.57,58 However, et al.66 The reason for this is that rapid aging is subjected to
compared with new battery integration applications, secondary uncertain aging mechanisms, which are difficult to quantify.
use of decommissioned batteries adds work in disassembly, Therefore, the aging performance experienced in the second life
detection, and sorting. Therefore, technical routes have might vary considerably, depending on the SOH level of the
gradually been abandoned because of their low economy. battery after the first use and its first life history.
M https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 11. (a) Li-ion battery pack energy usage (cumulative energy demand) for phases of the battery pack life. (b) Life cycle impact assessment
indicator results for 1 kWh of power delivered by the Li-ion battery pack cascaded use global warming potential (GWP) indicator. (a and b) Reprinted
with permission from ref 67. Copyright 2017 Springer Nature. (c) GWP impacts of an EV LIB with cascading reuse. (The dotted line reflects the
impact of the EV LIB life cycle with no reuse in stationary application.) Reprinted with permission from ref 70. Copyright 2017 Springer Nature. (d)
Life-cycle CO2 emissions associated with the defined scenarios for 3 paths. Reprinted with permission from ref 71. Copyright 2014 Elsevier.
4.3. Environmental Indicators and fossil-resource depletion potential. The calculations showed
It is thought that secondary use of EV batteries might alleviate that all impact indicators associated with the battery production
the burden of manufacturing a new battery or ultimately phase are greater than those for phases except for the fossil-
improve resource utilization. To accurately determine the resource depletion potential indicator. Notably, for the GWP
environmental benefits of secondary battery use, the environ- impact, the battery pack manufacturing phase generated the
most GHG emissions (∼40%), followed by the use and reuse
mental effects should be quantitatively assessed throughout the
phases (31% and 26%), which are also major contributors to the
entire life cycle of EV batteries. Two important issues of LCAs
GHG emissions (Figure 11b).67 In addition, they also compared
need to be addressed: (1) the contribution of secondary use to
the cascaded and conventional scenarios, based on an ICEV
the overall environmental impact of LIBs. (2) The reduced powered by gasoline. The six indicator results showed that the
environmental burden of reusing EV batteries. cascaded scenario had a lower environmental burden than the
In considering reuse of retired EV batteries, the full conventional scenario, except for metal as a depletion potential
environmental impact of EV batteries production, primary use, indicator.
repurposing, secondary use, and recycling must be accounted for In further investigations on the benefits of battery reuse to
in the LCA of batteries. Ahmadi et al.67 investigated the energy reduce the environmental burden of EV batteries, Cicconi et
consumption and environmental impact of EV batteries al.68 adopted an LCA approach to compare the environmental
throughout their life cycle in a cascaded scenario, including a impact of a PHEV battery (LFP) lifecycle with and without
second use in a stationary ESS and recycling. As illustrated in secondary use in a smart grid application. Three environmental
Figure 11a, the energy consumption of the primary and indicators were calculated: global warming, acidification, and
secondary use phases is higher than those of other phases, eutrophication. The LCA results showed that the environmental
representing the long-term battery applications, associated with gain was 25% considering a second-life scenario. However, they
use of the electricity mix. The battery manufacturing phase did not consider the collection, refurbishment, and trans-
energy usage is also high and associated with heat from natural portation of retired batteries, which will have a certain negative
gas and the electricity grid mix used for battery production. Six environmental impact. The environmental benefits of reuse of
indicators were calculated for the environmental impact EV batteries (LMO type batteries) in household energy storage
analysis: global warming potential (GWP), particulate matter for peak shaving and load shifting were also studied by Faria et
formation potential, freshwater eutrophication potential, photo- al.69 The following four impact categories were assessed for
chemical oxidant formation potential, metal depletion potential, LCA: abiotic depletion, acidification, eutrophication, and global
N https://dx.doi.org/10.1021/acs.chemrev.9b00535
Table 2. Main Second Life Battery R&D Projects73−75
Installed
battery
Country Project name/Partners Application scenario/Objective capacity Reused EV batteries Time
EU Bosch Second Life Batteries/BMW/Vattenfall The smart grid application of the electric utility Vattenfall in Hamburg 2 MW/ BMW i3 2015
2MWh
Chemical Reviews
BMW/Vattenfall Household energy storage 26.4 kWh BMW i3 2016

Daimler second Life Storage-The Mobility House/ The world’s largest second-use stationary storage with 13 MWh output made from around 1,000 used 13 MWh Smart Fortwo 2016
Recycling plant vehicle batteries demonstrated the potential in the reuse of vehicle batteries.
Catalonia Institute for Energy Research (IREC) B2G Exploring uses of second life EV batteries 23 kW retired EV batteries Not
mentioned
United Peak Shaving Battery at BMW Technology Demand Response programs, Peak Demand Shaving, and Photo-Voltaic Energy Storage, and 100 kW MINI E (LFP Not
States Uninterruptable Power Supply for power outages batteries) mentioned
UCSD BMW second Life EV Energy Storage System/ The micro grid of the University of San Diego/integrated with PV solar and possibly fast EV DC 108 kW MINI E 2014
UC San Diego charging
PHEV/EV Li-Ion Battery Second-Use Project/ Identify, assess, and verify profitable applications for the second use of PHEV/EV Li-ion traction Not Acquire Aged Li-Ion 2010
National Renewable Energy Laboratory (NREL) batteries to reduce the cost and accelerate adoption of PHEV/EVs mentioned Batteries
Japan EnerDel & Itochu Developing the advanced battery systems for a residential smart grid energy storage project Not EnerDel’ s lithium-ion 2010
mentioned battery systems
Nissan/Eaton A new residential energy storage unit 4.2 kWh retired Nissan Leaf 2014
battery
China Henan Electric Power Company Energy storage batteries 128 kWh Retired LFP batteries 2012
State Grid Corporation Fast charging station 175 kW Retired LMO 2014
batteries
Power Company Communication base station 1.5 GWh Retired LFP batteries 2015−2018
O
pubs.acs.org/CR
Review

https://dx.doi.org/10.1021/acs.chemrev.9b00535
warming. These LCA results show that the environmental of the appearance and performance by nano-CT to qualitatively
benefits from reuse are strongly related to mix of electrical power analyze the internal three-dimensional structure, establishing an
generation and additional efficiency losses in the battery. Sathre electrochemical model, and analyzing the internal performance
et al.66 verified that second-use of retired PEV batteries rather state by external electrochemical parameters. Recently, some
than natural gas-fired electricity in the California energy system intuitive technologies have been developed, such as a contact-
might reduce GHG emissions. The 7 Mt CO2 per year avoided type ultrasonic nondestructive testing technology, which can
in 2050 would account for 1.5% of the current total GHG rapidly and accurately detect the SOC and SOH of the cell
emissions of 460 Mt CO2 per year and a 14% reduction for the through correlation of ultrasonic signals with electrochemical
electricity generation sector. performance, and nondestructive and noncontact screening
Additionally, Richa et al.70 investigated the environmental methods. Detection methods for battery modules are relatively
impacts of the addition of reuse and made a direct comparison of effective and can detect Li battery growth without opening the
reused LIB to new Pb-acid battery systems for stationary energy battery module to reduce the risk of “dead Li” and short circuits.
storage. The results reflect that the reuse of a retired EV LIB in However, there is currently no mature technology or equipment
the stationary application could reduce GWP by 15% compared capable of detecting and screening battery modules.
with that without stationary use (Figure 11c). It was estimated After screening, battery modules will be reorganized, based on
that the refurbishing of LIB can reduce 12 to 46% GWP impacts a database compiling information on demand for secondary use,
compared with equivalent functionality Pb-acid battery. Ahmadi operational data, and the test parameters such as the material
et al.71 compared the environmental impact of three pathways of system, capacity, internal resistance, and residual cycle life. The
LIBs, including conventional vehicles (ICE) based on natural BMS of retired batteries are more comprehensive in terms of
gas power, PHEV with natural gas power, and PHEV with safety considerations than those for new batteries. Therefore, to
battery reuse. Among these, the reuse of PHEV batteries in peak reduce the security risk of discrete integration of retired
applications had lower CO2 emissions than other pathways. This batteries, new battery packs should consider the following
effect was particularly notable in a scenario where charging was aspects during reorganization: optimization of the module
performed by clean electricity and wind power, which reduced design connection to improve flexibility; adoption of intelligent
CO2 emissions by 56% (Figure 11d). In later studies, they time-division hybrid equalization technology; equipping suit-
confirmed that the energy efficiency fading has a more able current equalizers and an efficient temperature warning
pronounced influence on GHG emissions of the reuse phase system; and increasing module safety by thermal management
than that of the vehicle use phase. GHG emissions will increase and high-voltage monitoring. In addition, technologies such as
over time and a Li-ion battery pack will show high GHG cloud storage and blockchain might be used to improve the
emissions during an 8-year application in a BEV (approximately security of BMS and reduce the risk of illegally falsifying
2 tons), which is approximately 2 times as much as that of a counterfeit data for improper profit.
repurposed battery in a 10-year stationary application. Although 4.4.3. ESS Utilization. Thermal runaway of a battery is the
it is difficult to compare the environmental benefits of second- main cause of accidents, and precautions should be taken to
use of retired LIBs, in certain scenarios there are clear avoid such failure during secondary use of retired batteries.
environmental benefits. Abuse of the battery and leakage and oxidation of flammable
4.4. Security Indicators organic electrolytes might contribute to such failures. Relevant
safety standards have been developed to deal with emergencies
4.4.1. Disassembly and Storage. Decommissioned and abuses that might occur during battery use, including
batteries need to be reallocated for reuse, including disassembly Underwriters Laboratory (UL) standards, and the other
of the battery pack and module, removal of the external circuit, standards developed based on the UL standards, such as
casing and data sensor, and elimination of the scrapped battery. UL2054, UL1642, Japanese Industrial Standard (JIS)C8714,
The residual capacity, extremely high voltage, and unguaranteed and Chinese national standard (GB/T)18287. Although the
external circuit insulation performance and connection reli- safeguards and installed early warning systems implemented
ability, require disassembly of decommissioned batteries to be during screening and reorganization might effectively reduce
performed in an open space with safety protection measures. In and prevent the occurrence of thermal runaway. It is impossible
addition, disassembly processes should avoid irreversible to avoid failure of early warning systems caused by external force
damage to the battery itself. To ensure nondestructive and interference or short circuiting, which might result in fire or
safe disassembly, it is recommended to disassemble at the pack explosions. For secondary applications of decommissioned
or module level rather than the cell level owing to the soft batteries to energy storage systems, it is necessary to install
connection design between the modules, and the solder smoke detection devices at key locations and equip adequate fire
connection between the cells, dismantling at the cell level is protection facilities to avoid battery chain loss and prevent
neither technically or economically viable.51,56,61,69,72 Storage accidents from further expanding.
and transportation of decommissioned batteries should avoid
fire sources, long-term storage, long-distance transportation, and 4.5. Case Analysis
exposure to rain and external collisions to reduce the safety Retired LIBs have been used in multiple fields, such as mobile
hazards. power sources and stationary ESS. Many enterprises, research
4.4.2. Screening and Reorganization. Retired batteries institutions, and local governments around the world have
pose risks from defects such as leakage, flatulence, internal short shown great interest in the second use of batteries. Table 2
circuit, damaged casing, insulation failure, and pole corrosion. summarizes the second-use battery projects developed by
Screening out batteries with good health, a long remaining life, enterprises and research institutions.73−75 Daimler is committed
and good consistency is critical to improving the safety of retired to building the world’s largest secondary use stationary storage,
batteries for ESS utilization. Conventional screening methods made from approximately 1,000 used vehicle batteries with a 13
are mainly based on single cells, including testing and evaluation MWh output, demonstrating the potential for reuse of vehicle
P https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 12. (a) Global warming, photochemical smog, eutrophication, acidification, and ozone depletion of a 10 kWh PHEV battery life cycle when the
car is used in Scandinavia. Reprinted with permission from ref 80. Copyright 2010 Elsevier. (b) Sensitivity analysis of the relations between number of
dismantling facilities and total ton-kilometers traveled (red curve) and between capacity of recycling facility and marginal cost (blue curve), for in-state
recycling using truck transportation. Reprinted with permission from ref 81. Copyright 2015 IOP Publishing Ltd. (c) Global Warming Potential
(GWP/kg CO2) of five companies’ recycling processes. Data derived from ref 82. (d) GHG and SOx reductions for different cathode materials
recovered from pyrometallurgical, indirect physical, and direct physical materials as compared to producing them from virgin materials. Reprinted with
permission from ref 85. Copyright 2015 Royal Society of Chemistry. (e) Estimated energy consumption for LiMn2O4 production via automotive
battery recycling. (f) Total estimated energy consumption (MJ/kg battery) of BEV batteries made from virgin materials; with recycled cathode
materials; with recycled Al; with recycled Cu; and with recycled cathode material, Cu, and Al by different recycling processes. (e and f) Reprinted from
ref 86. Copyright 2012 American Chemical Society.
batteries. Additionally, some automotive enterprises have Reuse of retired LIBs in China has been based on energy
started commercializing products with second life batteries.75 storage demonstration projects of power grid companies, which
Automotive leader Nissan and power management leader Eaton, generally use high-capacity batteries and have high safety
have designed the “x Storage” based on retired Nissan Leaf requirements. In 2012, the first domestic application of retired
batteries to make home energy storage reliable and affordable for batteries for energy storage was led by the Henan Electric Power
everyone.76 The “x Storage” system can give consumers control Company.74 This project focused on reuse of power battery
over when they use energy in their own homes. Similarly, BMW system integration technology, which was used to match peaks
and Vattenfall have jointly developed a home-base system called and valleys in the power grid, provide power support in
“SunBESSy”, which is a residential 26.4 kWh system based on emergency situations, and maximize effective use of photovoltaic
second-use batteries retired from BMW’s i3 EVs. and wind power generation. China has also studied the following
In addition to automotive enterprises, many research application scenarios: EV charging power stations, communica-
institutions and local governments have examined the viability
tion base stations, mobile car charging, and electric tricycles.
of secondary battery use. NEC Laboratories in the USA have
These scenarios require a relatively small battery capacity, have
used retired batteries for secondary purposes, such as powering a
attainable safety and reliability requirements, and are econom-
building during peak load hours and reducing their carbon
ically viable with a large market and good commercial prospects.
footprint.77 The University of California proposed a model and
simulation results for a photovoltaic array paired with a second Furthermore, communication base stations represent an
life battery pack to stabilize electrical grid interactions in appropriate application for retired LIBs. The China Tower
residential photovoltaic systems and reduce the overall company has approximately 2 million base stations and long-
residential demand placed on the electricity grid.78 These term stable demand for retired power batteries. On the basis of a
results have shown that reuse of retired LIBs with an energy single-station battery capacity of approximately 30 kWh
capacity of 13.9 kWh and a PV array with a power capacity of (equivalent to an EV with a capacity of approximately 62 kWh
1.44 kW can reduce grid demand by more than 70%. In addition, after decommissioning of LIBs), the company has capacity for
they verified the feasibility of installing second-use battery packs nearly 2 million retired EVs. In recent years, the company has
in an off-grid photovoltaic vehicle charging system (SPCS).79 tested retired LIBs to replace existing lead-acid batteries at more
The cost of a SPCS system based on a second life battery pack than 3000 base stations in 12 provinces across China, under
was estimated to be 50% lower than a system with the same different conditions, such as backup power, peak-filling, and
performance based on new LIBs. microgrid applications.
Q https://dx.doi.org/10.1021/acs.chemrev.9b00535
5. COMPREHENSIVE EVALUATION SYSTEM FOR LIB To further quantify the benefits of recycling for environment
RECYCLING and resource conservation, Dewulf et al.83 performed a detailed
LCA comparison of scenarios, which included recycling of
A comprehensive evaluation system for recovered LIBs should
battery waste and reuse in battery production versus virgin
select appropriate recovery methods through comparative
production. The battery recycling scenario combined a smelting
analysis of various aspects in the recycling process. Environ- process developed by Umicore with a hydrometallurgical
mental, economic, technological, and safety considerations process to produce NiSO4 and CoSO4. Production of 1 kg of
should be evaluated in recycling processes. cathode material required only 387.4 MJ of resources for the
5.1. Environmental Impact and Energy Analysis battery recycling scenario, whereas 795.4 MJ was needed for
For retired EV batteries, the full environmental impact of virgin production. Hence, battery recycling can recover 51% of
transportation, collection, dismantling, and recycling of batteries natural resources used in virgin production. In addition, they
must be considered in battery recycling processes. Trans- found that fossil resources and nuclear energy consumption
portation to recycling centers is a minor contribution compared were reduced by 45.3% and 57.25%, respectively, through a
with the production and use phases of LIBs (Figure 12a).80 battery recycling scenario. This research indicates the positive
However, appropriate transport is needed to reduce or eliminate effects of recycling on the production of battery materials. Dunn
the environmental impact of the process. Hendrickson and co- et al.84,85 found that production of cathodes, especially those
with Co and Ni, is a key driver of LIB cradle-to-gate
workers81 have indicated that transport by rail and truck can
environmental impact. They estimated that use of recycled
reduce transportation-related GHG emissions (23%−45%).
cathodes, Al, and copper (Cu) to produce LIB might reduce
Furthermore, they combined LCA and geospatial models to
GHG emissions by 54% compared with use of virgin materials.85
capture the expected infrastructure needs, characterize the
In addition, they estimated GHG and SO2 emissions from
material flows and emissions, and calculate damage to human
cathode materials produced from recycled materials obtained
health from the LIB recycling network in California. These through three recycling processes, including a pyrometallurgical
results showed that establishing more than two dismantling process (Umicore), an intermediate process (Retriev Tech-
facilities would likely reduce the return on investment. They also nologies), and direct recycling (Onto).85 As shown in Figure
examined pyrometallurgy and hydrometallurgy recycling 12d, GHG emissions for producing a LCO cathode material
systems (Figure 12b). They confirmed that optimal recycling using a commercial pyrometallurgical recycling process
technology and multimodal collection and transportation in the represent a reduction of 60%−75%. Recycled cathode materials
supply chain can alleviate the environmental and economic containing Co and Ni reduced GHG and SO2 emissions
burdens of LIB production. In comparison with virgin compared with production of cathode materials from scratch.
production, pyrometallurgical recycling processes can reduce Direct recycling by the Onto company has the potential to
the primary energy consumption and GHG emissions by 6%− reduce GHG and SO2 emissions.
56% and 23%, respectively. Hydrometallurgy recycling achieves Of course, the energy intensity of the recycling process must
greater savings of electrical energy and produces less air also be taken into account. Dunn et al.86 estimated the energy
pollution; however, pyrometallurgical recycling has clear expended to produce recycled LiMn2O4 from three different
advantages in terms of water consumption. processes. Figure 12e illustrates that the energy intensity of all
The entire recycling process is a combination of several three recycling processes will be lower than that of the virgin
recycling technologies, such as intermediate and direct physical LiMn2O4 production. Among these, hydrometallurgical pro-
processes, pyrometallurgy, and hydrometallurgy. To identify hot cesses consume the greatest amount of energy owing to
spots for environmental impact in different stages of the whole consumption of citric acid and hydrogen peroxide in the
recycling processes, Engel et al.82 applied LCA methodology to process. Hydrometallurgical and intermediate physical pro-
different recycling processes for EV LIB. Systems covering the cesses are more energy intensive than direct physical process
entire recycling processes for EV LIBs were studied for five because the combined demand for production of Mn2O3 and
different companies, including at least two technologies for LiMn2O4 accounts for 73% to 84% of the total energy
dismantling, mechanical treatment, hydrometallurgy, and consumption of the two processes. Figure 12f indicates that
pyrometallurgical process steps. These results indicated that when LiMn2O4, Al, and Cu are recycled in a closed-loop
the major environmental impacts of recycling processes are scenario, the total energy consumption can be reduced by up to
landfill of waste material, incineration of plastics, and 48% through direct physical recycling, because recycling
consumption of electricity, particularly for energy-intensive processes are usually performed at low-temperatures without
smelting processes. The main effect of hydrometallurgical consumption of additional chemicals.
processes on global warming is landfill, whereas the main effect 5.2. Economic Analysis and Security Evaluation
of pyrometallurgical processes is incineration of plastics.
Mechanical and hydrometallurgical treatments can recover Economic analysis of LIBs recycling processes determines the
more materials with lower energy consumption than pyrome- industrial application potential of the recycling technology.
tallurgical technology. As shown in Figure 12c, company 4 has Therefore, an economic analysis of the recycling processes is
necessary for different LIB systems. The current economic
the lowest environmental impact, followed by company 1.
calculation model for battery recycling is shown in eq 1, where E
However, the main drawback of company 4 is that it uses only
is the profit, R is the revenues of products, and CT is the recycling
pyrometallurgical recycling methods and lithium carbonate
process total cost.
cannot be recovered. Therefore, for environmental consider-
ations, future research should focus on low temperature E = R − CT (1)
processes, such as mechanical and hydrometallurgical processes,
or a combination of mechanical, hydrometallurgical, and The recycling process total cost should include the collection
pyrometallurgical methods. and transportation cost (CC&T), depreciation cost of equipment
R https://dx.doi.org/10.1021/acs.chemrev.9b00535
Table 3. Economic Assessments of Present Recycling Processes

CT R
Recycling
processes CD MC CP CW CL CC CT Products Prices(/t) E
10 t Spent NaCl-discharging $3.38 $0.67 $3.0 $100 $78 $290 $475.05 345.76 kg $12,514 $4315.83
LMO Crushing and $12.16 $2.4 $4.4 $0 $79 $0 $97.96 Li2CO3
batteries Screening
Vacuum pyrolysis $730 $144 $176 $0 $72 $0 $1122
leaching and $152 $27.87 $160 $113.6 $156 $0 $609.47 1.76 t $1430
evaporation Mn3O4
purifying $68 $13.33 $64 $0 $78 $0 $223.33
1 t Spent LFP NaCl-discharging $1.69 $0.33 $41.5 $0 $39 $0 $82.52 260.7 kg $1000 $196.03
batteries and dismantling FePO4
Leaching $3.34 $0.66 $40.5 $5 $39 $254.28 $342.78
Filtering, Drying $20.92 $4.16 $46 $2 $117 $0 $190.08 49.5 kg $12,514
and Sieving Li2CO3
Purification $30.38 $6 $24 $0 $39 $0.7 $100.08
Precipitation $1.65 $0.33 $20 $4 $39 $19.24 $84.22 56.1 kg $2060
Waste Al
foil
1 t Spent Drying $12.81 $2.53 $192 $0.4 $39 $35 $281.74 741 kg of $32021.63 $28016.19
LCO High temperature $546 $108 $264 $0 $39 $0 $957 Co3O4
powders roasting
Leaching and $7.05 $1.42 $2 $3.65 $39 $0 $53.12 456 kg of $12,514
filtering Li2CO3
Precipitation and $32.03 $6.33 $44 $5 $39 $0 $126.36
purification
(CD), electric power consumption (CP), cost of equipment recycling; Sun et al.88 analyzed the profit of selective leaching of
maintenance (MC), water consumption (CW), labor costs, and spent LFP batteries with acetic acid. After leaching, Al and iron
chemical reagent cost (CC) . The depreciation cost of equipment remain in the solid residue in the form of metal and FePO4,
and the cost of equipment maintenance can be estimated as respectively, whereas Li is extracted as Li+ in the leaching
follows: solution. For treating 1 ton of spent LFP batteries, about 330 kg
i spent LiFePO4 cathode scraps can be obtained in this study. The
CD = CO × (1 − r ) × revenue of the whole process, including NaCl-discharging and
1 − 1 + i −n (2)
dismantling, leaching, filtering, drying and sieving, purification,
MC = CO × 0.05 (3) and precipitation, was calculated to be $196.03. These
calculations might address concerns about low or even negative
where CO is the acquisition cost of equipment, r is the residuals profits from recycling spent LFP batteries. Lin et al.89 used an
rate of equipment (4%), i is the interest rate (10%), and n is the economic assessment to investigate the profit of the sulfation
service life (5 years). The cost of electric power, water, and labor roasting recycling of spent LCO powders. The profit of recycling
are calculated as eq 4 and 5: 1 ton of spent LCO powders was approximately $28016.19.
CP = P × T × Pe (4) According to the above analysis, the recovery of spent LCO
batteries is considered to be most valuable in terms of high prices
CW = V × PW (5) of Co and Li metal compound. Due to the high leaching reagent
CL = m × PL consumption and low value products, recovering LFP powders
(6)
produced lower revenue. However, recovering LMO powders
CP is the cost of electric power, T is the working time of producing low value products have higher revenue than
equipment, P is the equipment power (Kw), Pe is electricity price recovering LFP powders. That is because the recycling
for industrial uses ($0.2/kWh); V is the water consumption technology for recycling LMO powders is simple, requires low
(ton/day), PW is the water price for industrial uses (1/t); m is the energy consumption, and has no additional chemical con-
number of workers, and PL is the wage of per labor ($39/day). sumption.
Based on the above equations, the profit of the recycling Due to its complex recycling process, few studies have
process for three cathode materials was calculated in detail conducted detailed economic calculations of the entire recycling
(Table 3). The first cathode materials are mixed LMO/graphite process for NCM materials. For example, Wang et al.90 only
powders, which are recycled by a vacuum reduction roasting compared the cost of synthesizing NCM materials from spent
process. These recycling processes produced by Xu et al.87 NCM batteries by hydrometallurgical and coprecipitation
include NaCl-discharging, crushing and screening, vacuum technology and synthesizing NCM materials from virgin
pyrolysis, leaching and evaporation, and purification. Assuming materials. The cost of synthesizing NCM materials from virgin
10 tons of spent LMO batteries are processed per day, about materials was $16635/ton, whereas the cost using spent
2.836 tons of cathode powders are obtained after pretreatment, batteries was $6195/ton. According to the material balance,
and the calculated profit for this process is $4315.83, excluding they also calculated the profit of the whole recycling processes of
the cost of collection and transportation, the cost of the factory spent NCM batteries.91 A profit margin of $5013/ton was
construction, and revenues from other metals such as Al, Cu, and obtained without considering labor, equipment, and energy
Fe. The second is to explore the value of spent LFP battery costs. Pagnanelli et al.92 simulated the economics of two
S https://dx.doi.org/10.1021/acs.chemrev.9b00535
hydrometallurgical processes for recycling of Co, namely solvent installed in acid storage locations to manage any potential
extraction and carbonatation. The total investment for solvent dangers. Acid- and alkali-corrosion-resistant equipment is also
extraction is higher than that of carbonatation; however, solvent required.
extraction is more economical than nonsolvent extraction 5.3. Technology Evaluation
because the purity of coproducts obtained by solvent extraction
is higher than the purity of recovered CoCO3. Owing to their The goal of recycling processes is to maximize the conversion of
low prices and high leaching efficiencies, inorganic acids are waste into useful materials, as measured by recovery rates. The
widely used to recycle NCM materials in an industrial high recovery rates achieved by recycling technologies, as
hydrometallurgy method. Organic acids are also considered to discussed in our previous review paper, demonstrate the
be the most promising leaching reagents. Li et al.93 conducted an feasibility of these technologies. Here, we reclassify battery
economic analysis of a hydrometallurgy leaching process. By recycling technologies into two categories: material repair and
comparing the cost of leaching reagents and energy regeneration technologies and material extraction recovery
consumption, they found that H3PO4, HCl, HNO3, H2SO4, technologies.
oxalic acid, malic acid, acetic acid, and similar acids have 5.3.1. Pretreatment. On the basis of the multiple
advantages, in terms of their low cost. Therefore, choosing an components of LIBs, pretreatments are necessary to strip the
efficient and low-cost leaching reagent is key to reducing outer shell and separate various valuable contents for subsequent
recovery costs. convenient recycling. However, because of the potential hazards
In summary, different LIB systems have different recycling in spent LIBs recycling, which include electrical shock, fire,
values. Different recycling processes also offer different explosion, and chemical hazards, safe and efficiently separation
economic benefits. Choosing a suitable recycling technology, components are the main goal of the pretreatment process.
even for recycling of small volumes of batteries, can achieve good Therefore, pretreatments include inactivation treatments,
returns. For recycling of spent NCM batteries, high value dismantling, and separation. To minimize risks from the high
products can be obtained by hydrometallurgical technology with voltage and the high reactivity of components, an inactivation
low energy consumption. When recovered by pyrometallurgy, a treatment is first introduced, which includes discharging,94−97
Ni/Co/Mn based alloy is usually formed and further hydro- freezing with liquid nitrogen,98 or processing the batteries in an
metallurgical separation is required to obtain a single product. In inert atmosphere. Owing to the inconvenience and consumption
recovery of spent LMO and LFP batteries, only two major of resources in discharging, the latter two inactivation treatment
metals are present in the cathode materials. Therefore, vacuum methods are widely used in industrial scale processing. However,
reductive roasting, selectively leaching, and mechanochemical these methods ignore potential dangers during storage and
methods can be used to directly separate and recover target transportation. The stored spent LIBs should be completely
metals, to shorten the recycling process, and to achieve a high discharged before recycling, to release all stored chemical energy
recovery rate. and render the battery unreactive. Methods of discharging
In addition to economic, environmental, and technology include the use of an external resistor or submerging the battery
indicators, potential safety issues in the recycling process should into a salt electrolyte solution.
be considered. First, we note that before being dismantled, spent Dismantling and separation are usually categorized into two
LIBs should be completely discharged to prevent fire or types: manual pretreatment and mechanical pretreatment.
explosion during transport and storage. However, in industrial Disassembly in laboratory studies for a small single cell have
recycling processes, spent LIBs are crushed and screened under been conducted mainly through simple manual dismantling with
liquid nitrogen or inert gas without a discharging treatment. The knives and saws. Safety glasses, face masks, and gloves must be
crushing and screening processes should be performed in a worn for safety. After dismantling, the different components can
closed apparatus with an exhaust system to collect and recycle be separated for recovery. Usually, the cathode materials are
volatile electrolytes. Simultaneously, it is necessary to avoid attached to the Al foil after manual dismantling. The separation
contact with air or water in the crushing process and take safety of the cathode materials from Al foil and removal of organic
measures, such as an inert gas atmosphere. Dust contamination binder are also important in the pretreatment process, which
from these processes should not be ignored. increase the complexity of the recovery process. Commonly
Wastewater, waste gas, and solid waste are generated during used methods are solvent dissolution,99,100 NaOH dissolu-
recycling processes. A strict three-waste monitoring and tion,101,102 ultrasonic-assisted separation,103,104 and thermal
treatment system should be established to prevent secondary treatment105,106 methods. Manual dismantling processes
pollution and realize environmentally friendly recycling and minimize the effects of impurities on the obtained materials.
utilization of spent LIBs. For the pyrometallurgical process, However, low processing yields make these methods unsuitable
treatment of exhaust gases and solid waste must be considered. for industrial applications.
For high temperature processes, a well-designed furnace with an Industrially, mechanical pretreatment is preferable to manual
exhaust gas treatment device is essential to reduce risk. dismantling, especially when large LIB packs for EVs need to be
Compared with pyrometallurgy, hydrometallurgical processes disassembled into smaller modules or single cells. Owing to the
produce lower amounts of waste gases and solid waste; however, wide variety of LIBs, preliminary classification can reduce the
wastewater generated by these processes requires consideration. negative effects of different components and facilitate
Regulations should be formulated for wastewater recycling, such subsequent recycling. Separation methods include chemical
as purification of high concentrations of ions by reverse osmosis and physical methods. Given their different physical properties,
to achieve zero wastewater emissions. Additionally, strong acid the Al foil, Cu foil, steel, separator, cathode, and anode are easy
or strong alkali solvents should be avoided for safety reasons. In to separate through crushing and screening, achieved by gravity
the recycling process, the use of acid should be strictly separation and flotation.95,107−115 The principle of gravity
controlled, appropriate standards and precautions should be separation is that mixtures with different sizes and densities have
considered, and water sources and fire equipment should be different motion in certain separation media. Materials of the
T https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 13. (a) Schematic plot of the regeneration process of spent NCM cathode material. Reprinted from ref 122. Copyright 2018 American
Chemical Society. (b) Illustration of the crystal structure change of NCM523 after cycling and regeneration. The right scheme shows the atomic
arrangement of layered, spinel, and rock salt phases along the [1̅2̅1] zone axis (same as TEM images). Reprinted from ref 121. Copyright 2018
American Chemical Society. (c) Phase diagram of LiNO3 and LiOH (reproduced from FACT salt database). (d) Illustration of the relithiation process
for Li composition recovery via the eutectic molten salt approach (a.b.: ambient). (c and d) Reprinted with permission from ref 123. Copyright 2019
Wiley. (e) Schematic illustration for the regenerating process of anode material from scrapped batteries. (f) Cycle performance curves of regenerated
anode materials. (e and f) Reprinted with permission from ref 125. Copyright 2016 Elsevier.
same particle size and different components, separated by addition, hydrothermal reactions have also been used by Chen et
sieving and screening, can be effectively sorted by gravity al. to supplement the Li source and regenerate degraded NCM,
separation methods based on density differences. Low-density which has a complex composition, and LCO cathode particles
parts are mainly composed of separators, plastics, and Al foil. by heat treatment.120,121
The cathode and anode can be separated through a flotation Recently, Sun et al. developed a new method to improve the
process based on differences in wettability. Specifically, graphite performance of spent NCM by surface coating V2O5 (Figure
is hydrophobic and cathode materials are hydrophilic. 13a).122 These simple and green regeneration processes provide
5.3.2. Crystal-Structure Repair Technology. Crystal- a novel approach to using recycling scraps from spent LIBs.
structure repair technology, as a nondestructive repair Furthermore, Li et al. confirmed that methods of separating Al
technology, also commonly known as direct regeneration, refers foil and cathode materials, and the calcination temperatures play
to repairing the crystal structure and restoring the electro- important roles in the electrochemical performance of
chemical activity of the material without a leaching treatment. regenerated NCM materials.103 Scraps regenerated by NMP
Compared with material extraction recovery technologies, the solvent dissolution separation and calcination at 800 °C deliver
main advantage of direct regeneration is that it can reduce the the highest discharge capacities. This result is attributed to the
recycling cost and maximize the value of the recycled materials, PVDF binder mostly dissolving in the NMP solvent, formation
realizing a closed-loop for LIBs electrode materials. In of less LiF, and preservation of more active Li+. The scraps
nondestructive repair of cathode materials, commonly used regenerated through direct calcination at 600 °C show the best
methods include heat treatments or combined lithiation and cycling performances with the highest capacity retention of
heat treatments. One of the main reasons for failure of LIB 96.7% after 100 cycles at 0.2C. The improved electrochemical
cathode materials is the irreversible phase change caused by Li performances are attributed to the complete decomposition of
deficiency during multiple cycling. For such failed LIBs, some PVDF, which introduces more LiF that can protect the active
researchers have considered repairing the cathode materials by materials from side reactions of the electrolytes. Notably,
supplementing the Li source by different methods. Owing to the impurities are the main problem to be considered in direct
simple elemental composition of LCO, LFP, and NCM scraps regeneration processes. Chen et al.121 systematically studied
from industrial production, which have not been used for failure mechanisms of layered oxide NCM particles and
charging, direct solid-state calcination can be used to repair proposed a nondestructive process to directly regenerate
these waste powders with or without addition of Li2CO3.116−120 degraded NCM particles. After many charge−discharge cycles,
Studies have shown that this method can repair the crystal a scattered rock salt phase and spinel phase accompanied by Li
structure and promote good electrochemical properties. In losses were apparent at the surface of a NCM523 cathode, which
U https://dx.doi.org/10.1021/acs.chemrev.9b00535
was restored to a layered phase by lithiation and thermal oxygen-free roasting and wet magnetic separation, for in situ
annealing (Figure 13b). Through this direct regeneration recycling of Li2CO3, Co, and graphite from spent LCO/graphite
method, higher phase purity and lower cation mixing were batteries. The mixed materials were directly calcined at 1000 °C
achieved in the regenerated NCM particles. These improve- under a N2 atmosphere for 30 min and then converted to
ments offer a higher specific capacity, better cycling stability, and Li2CO3, Co, and graphite. On the basis of the slight solubility of
a higher rate capability similar to that of the pristine materials. Li2CO3 and the ferromagnetism of Co, the mixed products can
Subsequently, they proposed a low-temperature relithiation be separated by wet magnetic separation. They confirmed that
process to regenerate degraded NCM523 particles using graphite powder acts as a reducing agent during the roasting
eutectic Li+ molten-salt solutions (Figure 13c and 13d).123 process. To further reduce the temperature of calcination, they
This work may provide a basis for further research into the then developed an integrated process for in situ recycling of
reversible chemistry of various solid-state ionic materials to metals from spent LMO batteries by vacuum metallurgy.87 After
develop environmentally friendly and economically viable roasting at 800 °C for 45 min under vacuum, the mixed electrode
regeneration synthetic strategies. materials, including LiMn2O4 and graphite, were converted into
For anode materials, the damaged layered structure of Li2CO3 and MnO. An in-depth study indicated that the
graphite and SEI components remaining after cycling conversion mechanism of the mixed LMO/graphite powders
complicate the regeneration of spent graphite as the new under vacuum conditions involves collapse of the cubic spinel
anode material for LIBs. The purity requirement of battery- LMO, in which Li elements filling O-tetrahedra are released as
grade graphite is higher than 99.9%; however, Minor et al.124 Li2CO3. In addition, they also confirmed the feasibility of in situ
successfully proposed a method for reuse of anode material from recycling of Li2CO3 under vacuum from other spent LIBs
used LIBs as new anodes. These results showed that recovered including LCO and NCM batteries.
anode material had equivalent cycling capacity and lower first To further reduce the calcination temperature and increase
cycle capacity loss than those of virgin graphite anodes. This the recovery rate, researchers have used salt cosolvents to roast
performance was attributed to the Li intercalation being and recycle spent LIBs.134−136 Salt roasting, including sulfate
preserved in the recovered carbon. Zhang et al.125 established roasting, chlorination roasting, and soda roasting, have been
a self-made scale model line to regenerate anode material from widely used in ore fossil pyrometallurgy. The main principle is to
scrapped Li-ion power batteries through a heat treatment in air convert the metal oxide into a water-soluble salt by roasting the
and coating with pyrolytic carbon (Figure 13e). The aim of the metal oxide under the action of a flux. For instance, Wang et
heat treatment was to remove acetylene black (AB), styrene al.135 developed sulfate roasting to recover Li and Co from spent
butadiene rubber (SBR), and carboxymethylcellulose sodium LIBs. A mixture of LCO and NaHSO4·H2O was roasted at 600
(CMC). The regenerated anode material was heat-treated at °C for 0.5 h, all the Li in the roasted products was present in the
600 °C for 1 h and then coated with 6.885 wt % pyrolytic carbon, form of LiNa(SO4), whereas Co was closely related to the
and it exhibited an initial charge capacity of 343.2 mA h g−1 and proportion of NaHSO4·H2O in the mixtures. As the content of
capacity retention of 98.76% after 50 cycles, meeting require- NaHSO4·H2O was increased, the Co formed the following
ments for reuse (Figure 13f). Moreover, Nowak et al.126 compounds: LiCoO2 → Co3O4 → Na6Co(SO4)4 → Na2Co-
successfully demonstrated the possibility of graphite recovery (SO4)2. The calcined products were further separated and
from spent LIBs by treating the electrolytes. Three different recycled by water leaching and chemical precipitation. Under
extraction methods have been proposed: thermal evaporation of the action of simple salt roasting, the structure of the cathode
electrolyte; electrolyte extraction by subcritical CO2 and materials can be destroyed at relatively low temperatures. This
acetonitrile; and electrolyte extraction with supercritical CO2. process shows great potential for industrial applications.
These results suggest that the best recycling method is Leaching-Regeneration. Leaching-regeneration hydrometallurgy
electrolyte extraction with subcritical CO2 and acetonitrile, methods require low-temperature leaching and separation or
because the recycled graphite showed the best performance and resynthesis to recover spent LIBs. This technology shows
90% of the electrolyte, including the conductive salt, was industrial potential for recycling of spent LIBs based on
recovered. advantages in terms of high recycling efficiency, low energy
5.3.3. Material Extraction Technology. 5.3.3.1. Cathode. consumption, limited hazardous gas emissions, and high added-
Pyrometallurgical Extraction Method. Material extraction recy- value products. However, this approach also must overcome
cling technologies are commonly divided into two categories: difficulties including complex operational procedures and the
pyrometallurgical extraction methods and leaching-regeneration need for wastewater disposal to realize industrial application.
methods. Pyrometallurgical processes aim to recover or refine Leaching. Leaching is a common procedure used to dissolve
valuable metals from spent LIBs through physical or chemical metals into solution for further separation and recycling.
transformations at elevated temperatures. Early pyrometallur- Leaching processes can be divided into three types: acid
gical processes required high temperatures of approximately leaching, alkali leaching, and bioleaching. Because of its high
1000 °C, and common products were Co-, Fe-, and Ni-based leaching efficiency and low cost, acid leaching has drawn the
alloys; however, Li metal falls into the slag phase and must be most attention. Inorganic strong acid leaching reagents, such as
further leached and extracted.127 Current pyrometallurgical HCl,137−140 H2SO4,106,141−143 and HNO3144,145 can dissolve
technologies include two types: reduction roasting and salt almost all metals, albeit with associated production of toxic gases
roasting. Reduction roasting refers to separation and recovery of and acidic wastewater. To address the environmental problems
metals by converting high-valent metal compounds into low- associated with inorganic acid leaching, our research group146
valent substances under vacuum or inert atmosphere and has first proposed an environmentally friendly organic acid leaching
received extensive attention in recent years.87,128−133 The agent for recycling of spent LIBs. Compared with mineral acids,
electrode materials of spent LIBs can be converted into metal organic acids not only reduce exhaust emissions but also
oxides, pure metals, and soluble Li salts. Xu et al.130 first effectively alleviate adverse effects on the environment, owing to
proposed a novel environmentally friendly method, involving the biocompatibility and biodegradability of these acids.
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Table 4. Summary of Organic Acid Leaching Parameters Investigated in the Literature and Their Corresponding pKa and
Structure
Organic acids have similar leaching efficiencies to those of from spent LIBs. Ascorbic acid can act as a leaching agent to
mineral acid and the leaching efficiency of organic acids is mainly dissolve metals and as a reducing agent to reduce high-valent
determined by their acidity, which is defined by their acid metals.155 Given its relatively strong acidity and reducibility,
dissociation constant (pKa) and the functional groups of the
oxalic acid has also been used to leach and recover spent
organic acids (Table 4).147−152 In addition, the unique chelating
LIBs.156,157 Owing to the different solubilities of oxalate, lithium
coordination properties are convenient for subsequent recycling
processes. For example, organic acids such as citric acid,101,153 oxalate can be dissolved, whereas other metal ions, such as Ni,
malic acid,154 lactic acid,102 and maleic acid93 can be used as Co, and Mn, are recovered as precipitates, known as selective
leaching or chelating agents to resynthesize cathode materials leaching.
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Figure 14. (a) E−pH diagram for the Al−H2O, Cu−H2O, and Fe−H2O systems (25 °C, Al = 0.2 mol L−1, Cu = 0.2 mol L−1, Fe = 0.2 mol L−1). (b) E−
pH diagram for the Ni−H2O, Co−H2O and Mn−H2O systems (25 °C, Ni = 0.2 mol L−1, Co = 0.2 mol L−1, Mn = 0.2 mol L−1).
However, during typical leaching processes an excess and high Unlike acid leaching, alkali leaching cannot dissolve all the
concentration of acid is used to ensure high efficiency, which metals into solution because the alkali leaching mechanism is
results in a large amount of acidic wastewater to be treated. To based on chelation between ammonium ions and metal ions, and
reduce the amount of acid, shorten the recycling process, and not all the ammonia complexes are soluble in water. The
improve the leaching efficiency, new approaches including currently proposed alkali leaching includes ammonia (NH3),172
selective leaching,88,158 mechanochemical methods,159 ultra- ammonium carbonate [(NH4)2CO3],173 ammonium sulfate
sonic treatments,139,160 and electrochemical methods161,162 [(NH4)2SO4],174 and ammonium chloride (NH4Cl). Aside
have been proposed for recovery of spent LIBs. Commonly from direct acid leaching, bioleaching also converts insoluble
used selective leaching reagents include oxalic acid,163−165 metal oxides into soluble metal ions based on production of
phosphoric acid,166 H2SO4,158 and acetic acid,88 which have acids through microbial metabolism. Some bacteria possess the
been used to recover Li in spent LCO and LFP. For example, Li ability to produce mineral acids, whereas some kinds of fungi
et al.158 selectively immersed Li into a solution using near metabolites can produce organic acids to promote leaching
stoichiometric amounts of H2SO4 and H2O2 as oxidants, processes.175−180 For example, the chemolithotrophic and
whereas Fe and P remained in the leaching residue as FePO4. acidophilic Acidithiobacillus ferrooxidans bacteria can use
This is because the addition of H2O2 enhances the leaching elemental sulfur and Fe2+ as an energy source to produce
effect and oxidizes Fe2+ in LiFePO4 to Fe3+, thereby forming a H2SO4 and Fe3+ in the leaching medium.179 The fungus
precipitate of FePO4. To further verify the practicality of Aspergillus niger can dissolve metals from spent LIBs by
selective leaching for NCM materials, Zhang et al.156 developed producing organic acids, including oxalic, citric, tartaric, and
an innovative application of oxalic acid leaching to regenerate malic acids.176 Although bioleaching has considerable advan-
the NCM. After leaching for 10 min, more than 98.5% of Ni, Co, tages in terms of energy-saving and environmental protection, its
and Mn was recovered by forming oxalate precipitates and lower leaching efficiency and slow microbial culturing have
deposited on the surface of the spent NCM. Li remained limited its industry applications compared with direct acid
dissolved in the solution. The oxalate precipitates with leaching. Furthermore, some other substances with the same
unreacted NCM were calcined to regenerate NCM by addition acidic behaviors have been used in leaching metals from spent
of a certain amount of Li2CO3. The regenerated NCM after LIBs. Liu et al.181 used dichlorination of polyvinyl chloride
leaching (OA-10) exhibited a highest initial specific discharge (PVC) in subcritical water as a hydrochloric acid source to
capacity of 168 mAh g−1 at 0.2C, which is attributed to the recover Co and Li from spent LIBs. Over 95% of Co and nearly
formation of submicrometer-sized particles and voids, and 98% of Li were leached under the optimum conditions of a
retention of the optimal elemental composition in the temperature of 350 °C, a PVC/LiCoO2 ratio of 3:1, a time of 30
regeneration process. Mechanical approaches have been min, and a solid/liquid ratio 16:1 (g/L). Thus, waste PVC can
performed with cogrinding reagents such as ethylenediaminete- simultaneously be converted to chemical raw materials without
traacetic acid (EDTA),167 ethylenediaminetetraacetic acid releasing toxic chlorinated organic compounds.
disodium salt (EDTA-2Na), 168 and polyvinyl chloride Purif ication and Separation. Impurities, such as Al, Cu, and Fe,
(PVC),159,169 solid agents such as Al2O3170 and Fe,171 and might be present in cathode materials during manufacture of Li-
organic aids,157 followed by a leaching process using water or ion batteries and pretreatment and leaching processes in the
mineral acid. After ball milling, metal ions are easily leached even recovery of LIBs. Therefore, it is necessary to purify the leaching
at ambient temperature or formed soluble chelates. The solution to improve the purity of the recovered products. Such
improved leaching efficiency and mild leaching conditions are impurities are usually removed by chemical precipitation, which
attributed to the reduced particle size and a local temperature is based on the different solubilities of metal compounds at
increase under the action of the mechanical forces, which certain solution pH. Metal ion impurities usually precipitate at
promote destruction of the crystal structure and facilitate the relatively low pH, whereas transition metals precipitate at high
chemical reactions. pH. (Figure 14a and 14b) A reasonable approach is to first
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remove impurities to avoid contamination of the subsequent method for coextraction of metal ions from spent NCM
target metal recovery process. In addition, because the leachate. These results showed that almost 100% of Mn, 99% of
resynthesized cathode material is sensitive to impurity metals, Co, and 85% of the Ni were coextracted and separated with the
solvent extraction is typically used to remove impurities and use of D2EHPA in kerosene. After stripping and adjusting the
achieve satisfactory levels of purity. The mechanism of solvent element ratio, the coprecipitation method was used to
extraction is based on the different solubilities of metals or metal synthesize Ni1/3Co1/3Mn1/3(OH)2 precursors, which were
compounds in the two-phase system, normally an organic and then calcinated to resynthesize new NCM cathode materials.
aqueous phase. This approach represents a new strategy for extraction of
After purification, the metal ions in the spent NCM leachate multiple elements. Compared with chemical precipitation,
are Li+, Ni2+, Co2+, and Mn2+ and the spent LFP leachate extraction processes are normally performed at room temper-
contains Li+, Fe2+, and PO43−. To obtain pure metals or metal ature with a short extraction time, and in an acid solution state,
compounds, metal ions are separated by chemical precipitation to reduce energy consumption and the use of alkaline solvents.
and solvent extraction. As for chemical precipitation, based on However, these processes also have some disadvantages in terms
the different physical properties of Li+ and transition metal ions, of the complex operation process and high solvent costs. Future
the transition metal ions are first precipitated, followed by Li+. extractants should be inexpensive, environmentally friendly, and
To precipitate transition metal ions, the most commonly used reusable solvents.
precipitants are sodium hydroxide (NaOH),182 oxalic acid In addition to the conventional chemical precipitation and
(H2C2O4),183,184 ammonium oxalate [(NH4)2C2O4],185 sodium solvent extraction methods, other methods including adsorp-
sulfide (Na2S),186 and sodium carbonate (Na2CO3)187 to form tion, ion-exchange, and electrodeposition have also been used
insoluble precipitates, such as transition metal hydroxides, for the metal extraction separation. A promising adsorbent for Li
oxalates, sulfides, or carbonates. Then, sodium carbonate is manganese oxide derived from spinel lithium manganese
(Na2CO3),188,189 phosphate (H3PO4),190 and sodium phos- oxide, which can be modified by acid treatment and surface
phate (Na3PO4)191,192 are used as precipitates for Li+ to form coating to increase the adsorption capacity. Recently, a
lithium carbonate, phosphate, or fluoride. However, because of mesosponge γ-Al2O3 monolith has been proposed as an
the similar chemical properties of transition metal ions, it is absorbent to detect, selectively extract, and recover the Co2+
difficult to sequentially separate them from leachate by ordinary ions even at a low concentration level of approximately 3.05 ×
precipitation and avoid formation of coprecipitates. To address 10−8 M.206 For spent LIBs, the adsorption capacity can reach
this problem, one approach is selective precipitation. For 196 mg/g for Co2+ ions. The adsorbent can also be regenerated
example, Co2+ can be oxidized to Co3+ and selectively by HCl as a stripping agent to completely release and recover
precipitated as Co2O3·H2O by an oxidative precipitation absorbed Co2+. Electrodeposition refers to the electrochemical
reaction with sodium hypochlorite (NaClO).193 Additionally, deposition of metals in leachate, which relies on the additional
Mn2+ can be oxidized to Mn4+ and selectively precipitated as energy provided by the two electrodes to induce redox
MnO2 through a redox reaction with potassium permanganate reactions.207−209 However, because of the high consumption
(KMnO4).140 These approaches can be explained by overlap of electrical energy, electrodeposition has not been widely used
between the stable areas of Ni2+ and Co(OH)3 in the E−pH for recycling of spent LIBs.
diagram, which might shift with temperature changes. Resynthesis. Compared with separation-based methods for
Furthermore, Ni2+ can be selectively precipitated as nickel recovery of metals from spent LIBs, resynthesis of materials is
dimethylglyoxime chelate and separated from the Ni, Co, and considered to be a more effective recycling method, which can
Mn mixed leachate with the dimethylglyoxime reagent (DMG, avoid complex separation processes, maximize recovery of
C4H8N2O2).140 cathode materials, and realize recycling of LIBs. More
Another approach is to separate metal ions through stepwise importantly, according to LCA analysis, this closed-loop
solvent extraction. Most research has focused on extraction of recycling method can reduce the energy consumption and the
transition metal ions, based on the differences of transition metal production costs of LIBs by producing high value-added
ion solubility in aqueous and organic phases. Commonly used products. Lossy leaching-regeneration refers to resynthesis of
solvent extractants for Co/Mn/Ni are 2-ethylhexyl phosphoric cathode materials from leaching solution by a sol−gel or
acid mono-2-ethylhexyl ester (PC-88A),137,194,195 bis(2,4,4- coprecipitation method. The main problem is selecting the most
trimethylpentyl) phosphinic acid (Cyanex 272),141,143,196−198 appropriate of these two resynthesis methods. Owing to the high
and di(2-ethylhexyl) phosphoric acid (D2EHPA).199−202 The leaching efficiency, the most commonly used leaching reagents
most commonly used stripping reagent is H2SO4. However, the are organic and inorganic acids. For organic acid leaching
unique chemical properties of lithium ions make solvent solutions, the best method for regenerating the cathode material
extraction difficult to achieve. More importantly, the extractant is the sol−gel method, because organic acids can also act as
can extract different substances in the presence of different chelating agents, not just leaching agents, particularly citric acid,
additives or under different extraction conditions. Furthermore, lactic acid, and malic acid. However, the complexing effect of
the extraction conditions, including equilibrium pH, extractant organic acids might change the precipitation properties of the
concentration, organic/aqueous (O/A) ratio, temperature, metal ions, making it difficult for them to precipitate in this
time, and extraction system, can affect extraction efficiency. system. Therefore, few studies have focused on regenerating
The combination of multiple extractants can improve the cathode materials from organic acid leaching systems by a
selectivity and extraction efficiency in complex leachate systems coprecipitation method. In addition, sol−gel methods can
through synergistic effects.195,203,204 However, for complex uniformly mix all metal ions, including lithium ions in the LIBs.
systems, multiple extraction stages and stripping stages are As described by Li et al.,101 after leaching of mixed spent cathode
required to separate transition metal ions with similar chemical materials under optimal conditions by citric acid, the molar ratio
properties. Recently, to avoid the complex extraction and of Li:Ni:Co:Mn and the molar ratio of total metal ions to
separation of Ni, Co, and Mn, Yang et al.205 developed a new chelating agent in the leaching solution were adjusted to be
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3.15:1:1:1 and 2:1, respectively. This solution was then used to recovery of 99.4 wt % Li was achieved with the use of 3 M HCl at
prepare an amorphous gel precursor by evaporating the solution 80 °C for 90 min with a S/L ratio of 1:50 g/mL. These results are
at 80 °C, followed by a two-step thermal treatment to form the attributed to the fact that Li2O, ROCO2Li, and CH3OLi are
new NCM. The resynthesized NCM showed better electro- water-soluble, whereas the other materials are hardly soluble in
chemical performance than that of NCM synthesized from a water. Spent graphite retains its original characteristics and
virgin salt solution. This better performance is attributed to Al configuration with a better crystal structure after acid leaching.
doping in the resynthesized material, which formed strong Al− Moreover, Bajaj et al.217 observed that 99.9% of Li can be
O bonds that maintain the structural stability during insertion/ recovered using water as leaching agent with 100 g/L pulp
extraction of Li. density at room temperature, which is based on the salts Li2CO3
For nonorganic acid leaching solutions, both the sol−gel and (1.29 g/100 mL), LiF (0.134 g/100 mL), and other Li salts
coprecipitation methods can be used to regenerate cathode being soluble in water at 25 °C. Therefore, it is also necessary to
materials. However, an additional chelating agent is required for recycle Li remaining at the spent anode.
resynthesis by sol−gel methods making these unsuitable for Owing to the conductivity, adsorption, and other physical and
large-scale applications. However, coprecipitation has been chemical properties of carbon materials, spent anode materials
widely used in industry because it allows homogeneously mixing can be modified for applications in many areas, including
and coprecipitation of a variety of transition metal ions at the adsorbents, catalysts, supercapacitors, and high-value gra-
molecular level. After coprecipitation, the Li+ remaining in the phene.218−225 On the basis of the adsorption properties of the
solution needs to be separately recovered by successive carbon materials, Yao et al.218 found that spent anode carbon
concentration and precipitation, which is based on the different materials could be used for treatment of wastewater after
chemical properties of Li and transition metals. Therefore, the modification. Adsorbents for phosphates and Mg-enriched
coprecipitation method is not suitable for recycling LIBs carbons were obtained from spent LIBs based on concentrated
containing two main metals, such as LCO, LMO, and LFP nitric acid oxidization and magnesium nitrate pretreatment with
batteries. The coprecipitation of NCM leaching solution is a 95% removal rate. The graphitized carbon materials from spent
usually performed in a hydroxide or carbonate system with a LIBs were modified with nanostructured Mg(OH)2 on their
stable pH of 8−11 and at a high concentration of transition surface with a high adsorption capacity of 588.4 mg/g.
metal ions of 2 M. Therefore, a low concentration leaching Phosphate adsorption was achieved by precipitation of P to
solution of the transition metal can be concentrated by form Mg3(PO4)2·8H2O and MgHPO4·1.2H2O nanocrystals on
evaporation. In addition, trace amounts of Cu (2.5%) and Mg the surface of the adsorbent. Moreover, the MnO2-modified
impurities have been shown to improve the electrochemical graphite sorbents based on spent LIBs were used to treat heavy-
performance owing to occupation of Mn sites by Cu and doping metal-contaminated wastewater with high removal rates of
of Co sites by Mg, resulting in a slight change of the lattice 99.9%, 79.7%, and 99.8% for Pb 2+ , Cd 2+ , and Ag + ,
parameters during Li insertion/extraction.210,211 respectively.220 The removal of heavy metals by MnO2-modified
Aside from cathode materials, many researchers have graphite sorbents was achieved through ion exchange of
examined syntheses of other high-value-added products, such hydroxyl groups.
as metal−organic frameworks (MOFs),212 catalysts Co3O4,213 Although challenging, there is great potential to synthesize
and Co ferrite precursor (CoFe2O4).214 Notably, Perez et al.212 high value products from spent materials. For example, Fan et
developed an innovative approach to synthesizing metal− al.222 reported a new strategy for recycling used anode graphite
organic frameworks (MOFs) from a simulated LIBs waste to prepare graphene sheets by sonication assisted liquid-phase
aqueous solution by precipitation. Metal−organic frameworks exfoliation. Those results showed that sonication assisted
(MOFs) are a unique class of porous crystalline materials, exfoliation efficiency of used anode graphite was 3 to 11 times
synthesized from metal ions and organic ligands. MOFs have as effective as that from natural graphite, with a highest mass
aroused broad interest and shown great potential in catalysis, gas yield of 40 wt %, owing to the reduced interlayer forces after
storage, gas separation, sensing, pollutant control, and electronic cycling. The conductivity of the recovered graphene reached
devices. Through the use of 1,3,5-benzenetriphosphonic acid 9100 S m−1. Similarly, Natarajan et al.226 converted spent
(BTP) in an organic solvent (DMF) as the organic ligand, 80% graphite into reduced graphene oxide (rGO) as a supercapacitor
of the Mn was selectively precipitated as Mn-MOFs at 150 °C material with the use of Al or stainless steel (SS) as a reducing
for 2 days, leaving only Co and Ni in solution. This work agent in the presence of HCl. Among the prepared rGO, Al-rGO
provides a new strategy for recycling metals in spent LIBs. at room temperature showed a high specific capacity of 112 Fg−1
5.3.3.2. Anode. Considering the rapid increase in the number at a current density of 0.5 Ag−1, which was attributed to its high
of spent LIBs, it is believed that recycling of the anode material degree of reduction and porous nature. They proposed a new
has considerable economic benefits and might reduce potential strategy for recovery and utilization of graphite and polymer
environmental pollution. The main valuable components of materials from spent LIBs for synthesis of polymer−graphite
spent anodes are the Cu foil, the graphite carbon material, and Li nanocomposite thin films.227 This study has focused on the
residue, which comes from charging and discharging process and synthesis of polyethylene (PE), polypropylene (PP), and
the stable SEI layer at the anode composed of Li2O, ROCO2Li, graphite composite thin film (PE/GRx and PP/GRx).
LiF, Li2CO3, and CH3OLi.215 Owing to the low bonding force Compared with neat PP and PE, the tensile strength of PP/
between graphite carbon particles and Cu foil, the Cu foil is GRx increased from 3.4 to 33.9 MPa and that of PE/GRx from
easily separated and recovered from the anode by physical 3.0 to 38.1 MPa. Similarly, the conductance of the PP/GRx and
methods such as crushing, screening, and other mechanical PE/GRx nanocomposite thin films was 5−6 orders of magnitude
separation processes.216 For the Li residue, Guo et al.215 higher than that of neat polymer thin films. In summary,
reported an acid leaching process with HCl to recycle Li from recovered graphite might be a good substitute for commercial
anodes of spent LIBs. A high leaching efficiency of 84% was graphite in the synthesis of graphene and nanocomposite thin
achieved in deionized water, whereas the highest leaching films. This substitution might decrease the quantity of solid
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Table 5. Current Industrial Recycling Processes of Spent LIBs
company technology Feature/process Final products location
Accurec Pyrometallurgy Collecting the organic solvents in electrolyte by vacuum pyrolysis; recovery of Li by vacuum evaporation; Co alloy, Li metal Germany
AEA Hydrometallurgy Using organic solvent to remove electrolysis and binder (PVDF); recovery Co in LiOH solution by electrodeposition Co2O3, LiOH UK
AkkuSer Ltd. Pyrometallurgyand two-phase crushing line is designed; magnetic and other separation methods follow it; scrap is then delivered to smelting plants and leaching Meal powder Finland
Hydrometallurgy
Chemical Reviews
Batrec AG Pyrometallurgy The spent LIBs are stored and shredded under CO2 atmosphere Co, MnO2, Ni- Switzerland
base alloys
Brunp Hydrometallurgy hydrometallurgical methods including leaching, purification, solvent extraction and resynthesis of materials Cathode materials China
GEM Hydrometallurgy hydrometallurgical methods including pretreatment, leaching, purification, solvent extraction, and the resynthesis of materials Cathode materials China
Glencore Pyrometallurgyand Combines pyro- and hydrometallurgy methods Alloy (Co/Ni/ Switzerland
Hydrometallurgy Cu)
IME Pyrometallurgyand Collecting electrolyte through evaporation and condensation; separating particles with magnetic separation; Co-base alloys produced by Li2CO3, Co-base Germany
Hydrometallurgy melting small particles in an electric arc furnace; Li2CO3 is obtained by dissolving the slag alloys
Inmetco Pyrometallurgy Scrap processed in a rotary hearth furnace and further refined in an electric arc furnace Ni-base alloys USA
JX Nippon Mining Hydrometallurgy Solvent extraction Ni/Co/Mn/Li Japan
and Metals
Mitsubishi Pyrometallurgy Freezing and disassembling under cryogenic liquid nitrogen environment; LiCoO2 is obtained by burning; the exhaust gas is absorbed by LiCoO2 Japan
Ca(OH)2
Onto Technology Direct recycling CO2 supercritical fluid Cathode materials USA
Recupyl Hydrometallurgy Crushing under inert gas atmosphere Co(OH)2, France
Li2CO3 or
Li3PO4
Retriev Technology Hydrometallurgy Disassembling under cryogenic liquid nitrogen environment Co, Li2CO3 USAand
AA
(Toxco) Canada
Rockwood Lithium Hydrometallurgy Combines similar mechanical and hydrometallurgical methods Co oxide, Li oxide Germany
GmbH
Sumitomo and Pyrometallurgyand The electrolyte and plastics are removed through calcination; pyrometallurgical process is used to recover alloy containing Co−Ni−Fe; Alloy (Co/Ni/ Japan
Sony Hydrometallurgy hydrometallurgical process is conducted to recover Co Fe), CoO
pubs.acs.org/CR
Umicore Pyrometallurgyand Ultrahigh temperature without pretreatment of LIBs; recovery of alloys containing Ni and Co by leaching; energy recycling CoCl2, Ni(OH)2 USA
Hydrometallurgy
Review

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waste, reduce potential pollution, and achieve high value-added These results showed that extraction pressure is the major
products. factor contributing to electrolyte extraction and the extraction
5.3.3.3. Electrolytes. Most research has focused on recycling yield was 85.07 + 0.36% under the operating conditions of 23
of cathode and anode materials, while neglecting recycling of MPa, 40 °C, and 45 min. In a following study, they investigated
electrolyte. The electrolyte, another important source of Li, is the influence of the physical properties of carbonate-based
composed of the organic solvents and toxic Li salts, which pose electrolyte on supercritical CO2 extraction behavior.233 They
environmental risks and require proper handling. Aged electro- confirmed through gas chromatography that polarity was the
lytes are not only present in a liquid form in the battery but also main factor controlling the extraction process of carbonate.
penetrate and become immobilized on the electrodes during Differences in the extraction behavior, yield, and ordering of
cycling, making them difficult to extract and collect. The physical extracted components were caused by variation of physical
and chemical properties of electrolyte components, including properties, including pressure, temperature, and time. These
volatility, inflammability, and toxicity complicate the recycling variations are explained by the polarity changes of supercritical
process. Despite these difficulties, electrolyte recycling has also CO2. Within a certain scope, increasing pressure or lowering
made some progress both in industry and the laboratory. In the temperature can enhance the polarity of supercritical CO2.
AEA technology recycling process, electrolyte is extracted with a To achieve closed-loop LIB electrolyte recycling, Dai et al.234
suitable solvent.228 In the Accurec recycling process, the developed a process for LIB electrolyte recycling, based on
electrolyte is collected by a vacuum heat treatment below 250 supercritical CO2 extraction, resin, molecular sieve purification,
°C followed by condensation.229 and component supplementation. Among the four main organic
Extraction is one of the most promising methods for components detected in the electrolyte extracts, the extraction
electrolyte recycling from spent LIBs. The first method for the yields of linear carbonates, EMC and DEC, were higher than
electrolyte recycling involves extraction with organic solvents. those of cyclic carbonates, VC and EC, which might be explained
Several organic solvents have been used to extract spent by polarity theory, as discussed in earlier research. Owing to the
electrolytes. However, compared with organic solvent extrac- sensitivity of the electrolyte properties to hydrofluoric acid (HF)
tion, extraction with supercritical CO2 avoids introducing and water, the extracted electrolytes must be purified by
impurities into the electrolyte and hazardous emissions and consecutive passage through anion exchange resin and
simplifies separation of the extracted products for reuse. molecular sieves so that the content of HF and water meet
Importantly, supercritical operations of CO2 are relatively mild China Chemical Industry Standards. After addition of
and thus suitable for extracting heat sensitive substances, such as supplemental components, the reclaimed electrolyte exhibited
LiPF6, in the extract or the raffinate phase. In an early study, a high ionic conductivity of 0.19 mS·cm−1 at 20 °C, and its
Nowak et al.230 first used supercritical helium head pressure application potential was confirmed by use in an Li/LiCoO2
carbon dioxide (sc HHPCO2) to extract electrolyte from the half-cell, which presented an initial discharge capacity of 115
spent LIBs in a simple autoclave setup. The extracts were mAh·g−1 with a capacity retention of 66% after 100 cycles at
analyzed by gas and ion chromatography, and solvents including 0.2C.
EC, DMC, and EMC were extracted. Moreover, the four aging
5.4. Current Industrial Recycling Process
products of electrolyte degradation, including diethyl carbonate
(DEC), dimethyl-2,5-dioxahexane dicarboxylate (DMDOHC), In the face of the large numbers of incoming retired LIBs, a new
ethylmethyl-2,5-dioxahexane dicarboxylate (EMDOHC), and cooperation has emerged among car companies, ESS utilization
diethyl-2,5-dioxahexane dicarboxylate (DEDOHC), were suc- enterprises, and recycling companies. For example, in 2018 μBW
cessfully extracted and identified. The concentrations of these announced the formation of a joint technology alliance with
solvents were related to the SEI growth on the negative Umicore and Northvolt to promote the sustainable use of
electrode. However, HHPCO2 is more expensive than conven- European EV power batteries. In the same year, Audi announced
tional liquid CO2, the recovery rate was relatively low, and the that it completed the first phase of cooperation in the battery
conducting salt LiPF6 was recovered only in trace amounts. To recycling strategy with Umicore and was working on develop-
overcome these drawbacks, they further developed a flow- ment of a closed loop for repeated use of LIBs and particularly
through method for quantitative extraction of LIB electrolytes the valuable raw materials. In China, China Tower has signed a
using supercritical or liquid CO2 with addition of different letter of intent for the construction of power battery recycling
solvents.231 These results showed that linear carbonates (DMC, systems with 11 new energy vehicle manufactures, including
EMC) were recovered in a higher overall yield with liquid CO2, FAW, Dongfeng, and BYD. This cooperation will help to
and cyclic carbonate (EC) most effectively extracted with establish a power battery traceability management platform and
supercritical CO2. The addition of solvents improved the enable retired battery ladder utilization and closed-loop
extraction of the electrolyte, particularly the Li conducting salt recycling.
LiPF6. The above results can be explained by the additional Current industrial recycling technologies and processing of
solvents having an intermediate polarity, which act as moderator spent LIBs are summarized in Table 5. The main industrial
between the very polar solvents and nonpolar CO2. A maximum recycling technologies can be divided into three categories:
recovery rate of 89.1 ± 3.4 wt % was achieved with liquid CO2 pyrometallurgy, hydrometallurgy, and a combination of pyro-
and the additional solvents acetonitrile (ACN) and propylene and hydrometallurgical methods. Initially, many companies used
carbonate (PC) (3:1) for 30 min and an additional 20 min with the pyrometallurgical method to recycle spent LIBs because of
liquid CO2 only. its simple operation; however, this process was not intended for
Dai et al.232 also focused on extraction of electrolytes from use in recycling of spent LIBs during their initial design. Only Ni,
spent LIBs with the use of supercritical CO2. First, the response Co, and Cu can be recovered as alloys, and Li is lost in the slag.
surface methodology was used to optimize the operational Owing to increasing demand for all these valuable metals, many
condition of the supercritical fluid extraction (SFE), which was companies have established a hydrometallurgical process to
applied to reclaim organic carbonate-based electrolytes.232 recover Li and obtain high-purity Co. As shown in Figure 15, the
AB https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 15. Flow chart of spent LIB industrials recycling processes: the pyrometallurgical technology developed by Accurec,235 the hydrometallurgical
technology developed by Recupyl,238 and the pyro- and hydrometallurgical technology developed by Umicore.236
overall industrial recycling process typically includes deactiva- energy is released from burning carbon materials and organic
tion, mechanical dismantling, magnetic separation, and matter can reduce the energy consumption and realize energy
pyrometallurgical or hydrometallurgical treatment. Representa- recycling to a certain extent. Safe and nontoxic filter residue
tive recycling processes are discussed in detail below. containing Al and Li can be used as an additive for construction
Accurec Recycling GmbH (Accurec) developed a vacuum materials. As the price of Li continues to rise, Umicore has
pyrolysis recycling technology based on traditional pyrometal- expressed an interest in recovering Li through additional
lurgy technology to recover metal elements from different hydrometallurgical processes. Alloys containing Ni and Co are
battery systems including Ni-cadmium batteries, Ni-metal further refined and converted to raw materials for battery
hydride batteries, Li-ion batteries, and alkaline batteries, having cathodes through a hydrometallurgical process, including acid
a recycling capacity of 7000 tons/year.235 The principle of the leaching, solvent extraction, and precipitation.
vacuum pyrolysis recycling process is based on the different Retriev Technology (formerly Toxco), founded in 1984, has
melting points of the metals and organic solvents. Electronics, been engaged in the battery recycling business for more than 20
plastics, and steel structures are removed by automated years.237 According to the structure and components of various
dismantling machines. The organic solvent is subjected to a batteries, the company has developed a complete set of recycling
vacuum heat treatment at 250 °C or less and condensed based technologies to ensure that each type of battery can be recycled
on the melting point of the organic solvent in the electrolyte. efficiently and with low environmental impact. For recycling of
The other portions of the batteries are fed into an impact mill. waste LIBs, Retriev Technology has used hydrometallurgical
Cu foil, Al foil, and iron-based alloy are separated by physical technologies to recover valuable metals. The battery packs are
separation. The other electrode materials are evaporated under first disassembled by a mechanical method and separated into
vacuum and condensed to recover Li. The other metals are cells, parts, and electronic circuits. To reduce the reactivity of
concentrated and recovered using existing industrial processes. single cells and prevent exhaust gas emissions, the single cells are
The Umicore VAL’EAS process combines pyrometallurgical frozen and placed in a liquid N2 environment at a low
and hydrometallurgical technologies to recover spent LIBs, temperature of −200 °C. The crushed products are divided
realizing a closed-loop from battery to battery.236 The recycling into three parts: metal-rich liquid mixtures, plastics, and metal
process can treat different types of batteries, regardless of the raw solid mixture containing elements, such as Cu, Al, and Co. The
materials, specifications, and forms. Specifically, the battery Li in the metal-rich liquid mixtures is recovered as Li2CO3 by
system is directly placed into a shaft furnace for metallurgical sequential addition of NaOH and Na2CO3 to the solution. The
processing without pretreatment. During the heat treatment plastics can be recovered directly and the metal solid mixture can
steps, material changes can be divided into three parts: the be used as a raw material for producing batteries.
electrolyte is evaporated at approximately 300 °C; plastics are In addition, Recupyl uses a highly efficient hydrometallurgical
pyrolyzed at 700 °C; the rest of the feed is reduced at 1200− process to recycle spent LIBs, including mechanical separation
1450 °C. The furnace is equipped with a gas purification system and chemical treatments.238 First, the batteries are broken under
to ensure zero emission of toxic dioxins or volatile organic a protective inert gas atmosphere. After magnetic separation, the
compounds, while collecting dust and solid particles. Compared plastics, steel, and Cu can be recycled directly. The remaining
with other pyrometallurgical processes, a clear advantage is that materials are successively leached with LiOH and H2SO4. After
AC https://dx.doi.org/10.1021/acs.chemrev.9b00535
Figure 16. (a) Cradle-to-gate GHG and criteria pollutant emissions per kWh of Focus BEV battery. Reprinted from ref 240. Copyright 2016 American
Chemical Society. (b) Contribution of main battery components to total GWP impact of each battery (FU = 1 kg of battery). Reprinted with
permission from ref 244. Copyright 2018 Elsevier. (c) Comparison of environmental impact indexes for the four kinds of batteries. Reproduced with
permission from ref 245. Copyright 2018 Elsevier. (d) Characterization results for the production of 1 kW h of Na-ion battery storage capacity and
contribution of the principal battery components to the overall impact per category. (e) Influence of the hard carbon precursor on the total
environmental impacts associated with NIB production, relative to the base case (sugar precursor). (f) Relative contribution to environmental impacts
per kW h of storage capacity in each assessed category. (d−f) Reprinted with permission from ref 247. Copyright 2016 Royal Society of Chemistry.
leaching, Cu, Al, and other impurities are removed as including heat, hydrothermal, and ultrasonic treatments, might
precipitates. By sequential addition of NaClO and an inert gas be used to recover surface damage of crystalline materials. The
(CO2), Co and Li are recovered as Co(OH)2 and Li2CO3, organic electrolytes can be extracted by supercritical fluid or
respectively. Other companies, such as GEM and Brunp have recovered by evaporation and condensation according to their
established a closed loop to realize recycling of spent LIBs based melting point. Organic solvents, used as binders and electrolytes,
on hydrometallurgical processes, which include leaching, should be environmentally friendly and easily degraded or
purification, solvent extraction, and resynthesis of cathode recycled. Compared with liquid organic electrolytes, solid
materials. electrolytes are easier to handle and recycle.
5.5. Recycling of Next Generation Batteries
6. LIFE CYCLE ASSESSMENT OF LIBS AND NEXT
It is necessary to consider recycling methods and processes GENERATION BATTERIES
suitable for future battery development projects during the
design stage. In our previous study, we showed that recovery 6.1. Life Cycle Assessment of LIBs
technologies for LIBs are the same as those used for lead-acid The life cycle of a battery consists of three phases: production,
batteries and MH-Ni and Cd−Ni batteries and can be use, and disposal and recycling. However, most LCA research
categorized as either hydrometallurgy and pyrometallurgy.37 only includes cradle to grave assessments owing to a lack of
Similar to LIBs, next generation batteries should be subjected to industrial recycling data or technology in the early stages of
discharge, automated disassembly, pulverization, and sieving to study, excluding the recycling stage.239−242 Even if the disposal
separate cathode materials and anode materials and collectors. stage is included in the assessment, this is usually a simple
In the pretreatment process, rapid, efficient, and safe incineration or landfill treatment.243 Researchers are primarily
disassembly is the primary task that recycling processes need concerned with the environmental impact of battery production,
to solve. Therefore, future battery assembly design should which is considered to be the most environmentally sensitive
consider the problem of disassembly. stage, followed by the use phase. Regarding the environmental
The main differences between next generation batteries and impact of battery production, three issues need to be addressed:
current LIBs will be in the composition of the battery used, (1) does the production of raw materials or battery manufacture
including the cathode, anode, and electrolyte components. dominate the environmental burden? (2) Which battery
However, the materials used in rechargeable batteries are simple component has the greatest environmental impact? (3) Can
substances or compounds composed of metals or nonmetals. the environmental burden be reduced through development of
Hydrometallurgy can be used to recover valuable metal elements alternative cathode materials and anode materials?
in battery materials. For functional materials (i.e., conductivity For the first issue, Kim et al.240 conducted a cradle-to-gate
and adsorption), consideration should be given to recycling of emissions assessment of mass-produced batteries in a
materials based on their function. Some repair methods, commercial BEV for a Ford Focus BEV. The functional unit
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Figure 17. (a) Climate impact per vehicle km for the two scenarios of Li−air batteries. (b) Climate impact per vehicle km with West European
electricity mix and with Swedish electricity mix for the use phase of Li−air batteries. (a and b) Reprinted with permission from ref 248. Copyright 2016
Elsevier. (c) Contributions of life cycle environmental impacts of the Li−S battery. (d) Life cycle impact benchmarking between the Li−S and the
NCM-graphite battery packs. (c and d) Reprinted with permission from ref 249. Copyright 2017 Elsevier. (e) Energy use and (f) climate change of the
Li/S cell production, showing cumulative improvements with bars and marginal stepwise improvements in percent. Scenario 4 has no influence in
energy use results and is therefore not shown in (e). (e and f) Reprinted with permission from ref 250. Copyright 2018 Elsevier.
in this study is 1 kWh of battery energy capacity. These results the main drivers for GWP are the production of the cathode and
showed that cell manufacturing is a key contributor accounting cathode binder. For different LIBs systems, discrepancies come
for 45% of the GHG emissions (see Figure 16a). The production from the cathode, because of the different mass shares of cathode
and manufacture of materials and components for batteries, current collector and cathode active materials.
including the cathode, anode, current collectors, electrolyte, The differences in LIB systems depend on the different
separator, and pouch materials, account for 19% of the GHG cathode materials. Therefore, the use of a suitable cathode
emissions. Additionally, cell manufacturing, cell components, material might reduce the environmental burden. Yu et al.245
and battery enclosure also dominate other pollutant emissions used the footprint family of indexes to characterize the
and account for 82%−92%. The contributions of main battery environmental impact of four battery production processes, as
components to the total GWP impact for each battery type are shown in Figure 16c. These results show that
shown in Figure 16b.244 The comparison is based on a functional LiFe0.98Mn0.02PO4/C batteries have a higher index value than
unit of 1 kg battery. A common component package, BMS, and that of C/LiFePO4 batteries indicating a higher environmental
energy (electricity and heat) demand account for 50%−60% of burden. This higher value is attributed to the small amount of
the total GWP impact. Other GWP impacts derive from Mn doping, which complicates the processing. The index values
components of the battery including anode, anode binder, of LiMn2O4/C are smaller than those of C/LiFePO4 batteries,
cathode, cathode binder, electrolyte, and separator. Note that indicating that the contribution of Mn to the footprint is lower
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Figure 18. (a) Elemental abundance in the Earth’s crust and Ocean. Data derived from refs 252 and253. (b) Availability of lithium sources worldwide.
Data derived from ref 13.
than that of Fe. Among the four battery types, the environmental emissions of NCM-Li batteries by improving the energy
burden of FeF3(H2O)3/C batteries is extremely small, owing to efficiency of the facilities.
the simple and environmentally friendly synthesis technology 6.2. LCA of Next Generation Batteries
and the low amounts of raw materials used. We conclude that
the environmental effects of Li are greater than those of Fe. In the above LCA of LIBs, battery manufacture dominates the
Therefore, exploring simple synthesis techniques to reduce the environmental burden. Therefore, there is a need to quantify the
use of heavy metals and identifying alternative materials are potential environmental impact for production of next
important directions for reducing the environmental burden of generation batteries. Current candidate replacement technolo-
LIBs. Li metal, which has a higher specific capacity than a gies have yet to be commercialized; hence, data are lacking and
conventional graphite-based cell, represents the most promising few researchers have assessed the life cycle. NIBs made with
advanced anode material for next-generation batteries. Wu et abundant, environmentally friendly and cheap materials have
al.246 compared the cradle-to-gate LCA of three batteries potential to be used as alternatives to LIBs. Peters and his co-
designed with a Li metal anode (NCM-Li), a silicon nanowire workers247 conducted a prospective LCA for production of
anode (NCM-SiNWs), and a graphite anode (NCM-C), NIBs, based on a layered transition metal oxide as a cathode
respectively. They found that a high specific energy anode material and hard carbon as the anode material on the battery
produces less pollution during battery production. The NCM-Li component level. The anode is the important factor affecting the
battery has a lower environmental burden than two types of LIBs GWP, FDP, and MEP, owing to the use of sugar as a precursor to
based on a 1 kWh storage capacity. However, NCM-SiNWs prepare the hard carbon (Figure 16d). Compared with existing
batteries, which have a higher specific energy than those based LIBs, the assessed NIB based on an energy capacity (1 kW h of
on graphite, also have a greater environmental impact than that storage capacity) shows promise for a lower environmental
of NCM-C batteries. This impact is attributed to extremely high impact (Figure 16e). They also found that reducing the
emissions of SiNWs preparation. There is potential to reduce environmental impact associated with the hard carbon
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Figure 19. (a) The resource consumption of LIBs cathode materials based on producing 1 GWh capacity. (b) Cobalt and lithium demand for EVs,
2017 and 2030 in New Policies Scenario and EV30@30 Scenario. (In the low cobalt scenario, NMC 811 makes up 90% of battery sales in 2030, with
the rest being NCA. In the high cobalt scenario, NMC 622 makes up 90% of sales with NCA the rest.) (c) Effect of change in battery chemistry on costs.
(Gr = graphite.) (d) Future cost of EES technologies at 1 TWh cumulative capacity. (b and c) Reprinted with permission from ref 7. Copyright 2018
International Energy Agency. (d) Reprinted with permission from ref 254. Copyright 2017 Springer Nature.
production for the anode could further decrease the environ- improvements include reducing the electricity consumption of
mental impact (Figure 16f). the cell production, sourcing renewable electricity, improving
Li−S batteries and Li−air batteries have been investigated for the specific energy, and shifting to low-impact carbon materials,
future EVs because of their high theoretically energy densities. which might reduce energy use and climate change impact by
Further LCA studies would guide and promote the sustainable 54% and 93%, respectively. As shown in Figure 17e and 17f,
development of these rechargeable batteries. Zackrisson et al.248 reducing electricity use during cell production lowers the energy
analyzed the LCA of Li−air batteries from cradle-to-grave to output by 21% and reduces the environmental impact by 55%.
facilitate their improvement. These results were similar to those An increase of approximately 67% in the Li/S battery specific
of LIBs, in that production-related effects dominated the energy would lead to a 54% reduction in energy use compared
environmental impact categories at the current level of Li−air with the base scenario. Therefore, reducing electricity use during
batteries (Figure 17a). However, as Li−air batteries develop, the cell production is the best solution to reduce the environmental
use phase has the greatest environmental impact and changing impact, and increasing the specific energy is the best solution to
the electricity mix might reduce this (Figure 17b). Moreover, reducing energy use compared with other improvements.
this study showed that the environmental impact of Li−air To date, no quantification of the potential environmental
batteries will be 11%−25% that of LIBs in the long term and impact of production of KIBs, Al-ion batteries, and Mg-ion
recycling of batteries can avoid 10%−30% of the environmental batteries exists. Given their similar battery composition to LIBs,
impact from battery production. we conclude that reducing or eliminating the heavy metal
Yuan et al.249 developed an LCA model to assess the life cycle content in the cathode active material and choosing environ-
environmental impact of Li−S batteries based on laboratory mentally compatible cathode and anode material resources will
experiments, industrial battery manufacturing processes, and be key objectives for reducing their impact. Additionally,
literature data, for a graphene sulfur composite cathode and a Li improving the energy efficiency of the manufacturing process
metal anode protected by a Li-ion conductive layer. As shown in and minimizing the required electronic components (i.e., cables,
Figure 17c, in the life cycle of a Li−S battery pack, the battery use BMS) might decrease the environmental impact of all
phase accounts for approximately 70% of both the GWP and rechargeable batteries.247 The use of alternative, water-based
FDP impact, followed by the battery production phase, which binders for the cathode could further reduce GHG emissions.251
contributes 28%−36%. Within the production phase, the GWP Therefore, developing environmentally friendly next generation
and FDP impact of Li−S battery cell assembly account for 60%, batteries would help to reduce the environmental burden of the
owing to intense use of electricity. In comparison with NCM- battery production phase, which is also linked with the
graphite LIBs, Li−S batteries have a considerably lower impact, development of future rechargeable batteries.
which can be attributed to the use of low impact bulk materials,
6.3. Resource and Economic Analysis
no heavy metal containing materials, and reduced Cu usage
(Figure 17d). Arvidsson et al.250 conducted an LCA study of The development of rechargeable batteries in the future might
energy use and contributions to climate change for Li/S provide a solution to meet the challenges of achieving high
batteries to determine potential for improvement. Possible energy densities in EVs and ESS, the feasibility of strategic
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resources must be considered, including element reserves, (such as a move to beyond Li-ion technology, which is not
production capacities, and geographical production concen- expected to become available until after 2030) might have a
tration. In the case of Li, as an inherent element of LIBs, Li serious effect.7 Therefore, researchers have been looking for
resources are distributed in different forms of mineral and brine alternatives to Co and Li of battery materials. From the
deposits; however, Li is not regarded to be an abundant element. economics of LIBs, moving from a cathode of a uniform content
The abundance of Li in the Earth’s crust is limited to 20 ppm,39 of NMC 111 to one where nickel atoms account for 60% of the
which is lower than those of Na, K, Mg, and Al (Figure cathode (NMC622) might reduce costs by 7% (Figure 19c). In
18a).252,253 Continuous development of LIBs has led to addition, electrical energy storage could play a pivotal role in
considerable increases in global exploration of Li resources, future low-carbon electricity systems and electrification of
which currently total more than 62 million tons. South American transportation sectors. To explore the economics of electrical
countries, such as Argentina, Bolivia, and Chile, account for 66% energy storage technologies, Schmidt et al. constructed
of the world resources and have higher quality deposits than in experience curves to project future prices for 11 electrical
the USA and China (Figure 18b).13 Sodium resources are all energy storage technologies.254 They found that capital costs are
low-cost and highly abundant salts including Na2CO3, Na2SO4, on a trajectory toward US$340 ± 60 kWh−1 for installed
and NaCl, which are more readily available and can also be stationary systems, US$175 ± 25 kWh−1 for battery packs, and
extracted from minerals and brine. Although soda ash (Na2CO3) US$135 kWh−1 for portable batteries once 1 TWh of capacity is
can be manufactured from salt and limestone, both of which are installed for each technology (Figure 19d). However, bottom-up
practically inexhaustible, synthetic soda ash is costly to produce assessments of material and production costs indicate that this
and generates environmental waste. Potassium is mainly present price range is not feasible before 2027−2040. There is no doubt
in the form of potash such as potassium nitrate, potassium that LIBs have experienced considerable cost reductions since
chloride, potassium sulfate, and potassic fertilizers. The their market introduction in the 1990s. Simultaneously, early
abundance of potassium resources in the Earth’s crust and development of LIBs has provided valuable experience for
oceans is slightly lower than that of Na (Figure 18a).252,253 subsequent battery production, achieving significant cost
Estimated world potash resources total approximately 250 reductions and performance improvements over the past
billion tons. Canada leads the world in potash production, with decade. These battery developments have made the develop-
approximately 38% of global production capacity. The world’s ment of Li-ion battery packs for EVs increasingly viable.
Al resources are expected to be 55−75 billion tons. For
magnesium, relevant compounds can be recovered from many 7. POLICY-ORIENTED RECYCLING MODE AND
sources and are globally widespread. The world magnesite RECOVERY STATUS OF SPENT LIBS
resources have been determined to be 12 billion tons.
Laws, regulations, and policies, as guiding or mandatory
In addition to the above-mentioned necessary metal elements,
documents, are essential for management and recycling of
some transition metal elements such as nickel, Co, and
spent LIBs. For the recycling of spent batteries, developed
manganese are also used in batteries. United States Geological countries including the USA, Germany, and Japan have already
Survey (USGS) reports, have revised identified world terrestrial established relevant legislation from the perspective of life-cycle
nickel and Co resources to 89 million and 25 million tons, management of batteries. China has also formulated policies for
respectively, in 2019. Extensive nickel and Co resources also are the management and recycling of spent LIBs.
found in manganese crusts and nodules on the ocean floor. More
than 120 million tons of Co resources have been identified in 7.1. Power Battery Ladder Utilization
manganese nodules and crusts on the floor of the Atlantic, Power batteries decommissioned from electric vehicles usually
Indian, and Pacific oceans. The majority of terrestrial Co have a residual capacity of more than 70% of the initial capacity,
resources are located in Congo and Australia. The world’s and a certain service life. After redetection analysis, screening,
manganese resources are large but unevenly distributed. and battery cell pairing, they might be used for other
Approximately 74% of the world’s identified manganese applications; for example, in fields where battery performance
resources are located in South Africa. According to the 2014 requirements are low, such as in a microgrid, for tasks such as
USGS global assessment of Cu deposits, globally identified Cu smoothing distributed power fluctuations and user-side demand
resources are 2.1 billion tons and undiscovered Cu resources are response. Through ESS utilization of batteries, the pressure of
estimated to be 3.5 billion tons. The world’s inferred resources large-scale batteries entering the recycling stage can be
exceed 800 million tons of recoverable graphite. In 2018, 70% of alleviated. Therefore, the costs of batteries can be effectively
the world’s graphite was produced in China. According to the reduced, which will promote development of the electric vehicle
2019 USGS Mineral Commodity Summaries, China, Brazil, and market.
Turkey are the top three holders of the world’s graphite reserves. Research on the ESS utilization of batteries has been ongoing
This amount is estimated to be greater than 230 billion tons of for some time. Some countries have already developed effective
iron and more than 800 billion tons of crude ore. battery recycling management measures. For example, the USA,
Resource consumption of LIBs cathode materials based on Germany, and Japan have successively introduced direct
production of 1 GWh is calculated and plotted in Figure 19a. subsidies for energy storage systems, including the USA self-
Cathode materials produced for NCM111 and LCO consume generation incentive plan (SGIP). The subsidy policy has a more
more Li resources than other cathode materials. By 2030, obvious effect on energy storage projects. According to SGIP,
changes in cathode chemistries will affect demand for Co more the California Public Utilities Commission supports power
notably than that for Li (Figure 19b).7 Battery manufacturers’ producers in installing energy storage technologies providing on
research and development will aim to increase the energy the spot funds for uses in ESS, based on capacity, charge and
density of cells, by transitioning from NMC111 to NMC622 and discharge efficiency, warranty period, and cost as assessment
NMC811 cathodes, which will have a major influence on indicators.255 At present, most countries are promoting use of
demand for Co. For lithium, only major battery design changes retired batteries in ESSs. Germany, the USA, Japan, and other
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countries have completed many successful demonstration and consumers to collect and submit spent batteries.261 In addition,
commercial projects due to their early start. Most of these the USA has performed considerable research on power cell ESS
projects involve energy storage, such as Japan’s “4R Energy,” utilization and recycling technologies, including evaluations of
which uses batteries that have reached the end of their useful life the economic benefits of battery recycling and upgrading of
for household and commercial energy storage. The German recycling technologies.
Bosch Group uses BMW’s pure electric vehicle decommissioned 7.2.2. Germany: Building a Complete Power Battery
power battery to build a 2MW Tan MWH large-scale Recycling System. Germany has made remarkable achieve-
photovoltaic energy storage system.75 The company FreeWire ments in its legal system, division of responsibilities, and
has developed a mobile electric car charging ESS for office areas, technical routes for battery recycling. According to directives
based on decommissioned used power batteries.256 such as the Waste Framework Directive (Directive 2008/98/
For domestic ladder utilization, at the beginning of 2016, the EC), the Battery Recycling Directive (Directive 2006/66/EC),
Ministry of National Development and Reform Commission, and the Scrapped Vehicles Directive (Directive 2000/53/EC),
the Ministry of Industry and Information Technology, and the Germany has enacted the Recycling Law, the Battery Recycling Act,
Ministry of Environmental Protection jointly issued the the Scrap Automobile Recycling Act, and other related recycling
“Technical Policy for Recycling and Utilization of Electric Vehicles laws.262,263 Under constraints of the relevant legal framework,
for Electric Vehicles (2015 Edition).”257 It is clearly stated that the the spent battery recycling system has a clear division of labor.
use of retired batteries should follow the principle of “recycling Producers, consumers, and recyclers in the industry chain have
after cascade”. This guiding policy for ESS utilization of batteries corresponding responsibilities and obligations. In addition, the
in China has played a guiding role in the production and producer responsibility extension system is emphasized. New
recycling of batteries. The Interim Measures for the Administration energy vehicle manufacturers such as Volkswagen and BMW
of Recycling and Utilization of New Energy Vehicle Power Batteries have actively performed recycling of spent batteries. The
issued by the Ministry of Industry and Information Technology German Ministry of Environmental Protection has funded
in February 2018 stipulates that use of spent batteries should demonstration projects using pyrometallurgical and hydro-
follow the principle of recycling after ESS utilization.258 This metallurgical recycling technologies to provide an in-depth
guidance is important for relevant companies aiming to establish analysis of the use of different recycling technologies for
a complete recycling system and promote development of batteries.
industry in an orderly and developed manner. However, the 7.2.3. Japan: The World’s Leader in Battery Recycling
guidance has not achieved all prospective goals because of a lack Technology. Affected by the scarcity of raw material resources,
of punitive provisions. State Grid, Chinese Academy of Sciences, Japan is a global leader in the recycling of spent batteries. Since
and other institutions have actively promoted ESS utilization of 1994, Japan has promoted a battery recycling program and
batteries. However, the technology is far from mature enough to established a recycling system for “battery production−sales−
be promoted on a large scale. Notably, there is still a certain gap recycling”. To regulate the development of the scrap battery
between the development of ESS utilization of batteries in China recycling industry, Japan has introduced corresponding laws and
and the world. Research and applications have only begun in regulations from three levels: basic law, comprehensive law, and
recent years and are still in the demonstration stage. special law. It is stipulated that new energy vehicle
manufacturers are obliged to recycle and dispose of spent
7.2. Valuable Metal Element Recycling
batteries. Vehicle manufacturers are encouraged to pay attention
Recycling of valuable metals is the next critical step after ESS to research into resource recovery related to automotive battery
utilization of batteries considering the economic value and recycling technology. Automobile manufacturers such as
environmental significance. A battery that has an attenuated Toyota, Nissan, and Mitsubishi have actively invested in
electrochemical performance owing to internal structural research and development of battery recycling. Frequent natural
damage cannot be reused; however, resources in these batteries disasters in Japan have promoted the use of emergency power
can be recovered by splitting. supplies. Under the impetus of automobile companies, house-
7.2.1. US: Establishing a Sound Legal Framework for holds and enterprises use decommissioned new EV batteries as
Battery Recycling. For recycling of spent batteries, the legal emergency power sources. This battery recycling model is based
system of the USA involves federal, state, and local levels. At the on production enterprise and thus promotes the original
federal level, licenses are used to regulate battery manufacturers innovation of the enterprise from the product development
and spent battery recycling companies. The production and and design stage and improves the recycling rate.
transportation of spent batteries is regulated through the 7.2.4. China: Introduction of Regulatory Documents
Mercury-Containing and Rechargeable Battery Management and Improvement of the National Standard Recycling
Act.259 At the state level, most states have adopted battery System. Since the growth of the battery recycling industry in
recycling regulations proposed by Battery Council International 2016, China issued policy documents, such as “Standard
(BCI) to guide retailers and consumers, through a price Conditions for the Comprehensive Utilization of Waste Energy
mechanism for participating in recycling of spent batteries. For Storage Battery for New Energy Vehicles.”264 These specifications
example, New York State Rechargeable Battery Law and provide specific and clear evaluation and review measures for the
California’s Rechargeable Battery Recycling Act require retailers industry, which are an important step for building a robust
of rechargeable batteries to reclaim consumers’ disposable national standard system in the field of power battery recycling.
rechargeable batteries without issuing a charge.260 At the local The four normative documents for dismantling and recycling of
level, most municipalities in the USA have developed power power batteries have proposed clear and operational industry
battery recycling regulations to mitigate the environmental norms and established a complete national standard system for
hazards of spent batteries. The American Battery Council the battery recycling industry.
International has enacted the Battery Product Management Act, The Code for Recycling and Dismantling of Vehicle Power
which created a battery recycling deposit system to encourage Batteries (GB/T 33598-2017) has strict requirements for safety,
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operation procedures, storage, and management of spent battery

recycling, which is conducive to standardization of recycling and
dismantling of vehicle batteries in China. The Vehicle Power
Battery Recycling Utilization Energy Detection (GB/T34015-
2017) standardizes battery appearance inspection, polarity
detection, voltage discrimination, charge and discharge current
discrimination, residual energy testing, and other detection
processes. This guidance provides a scientific approach for
assessing residual energy of EV batteries. The Automotive Power
Battery Coding rules (GB/T34014-2017) makes power batteries
uniquely identifiable so that they can be traced throughout their
life cycle. Specifications and Dimensions of Power Battery for
Electric Vehicles (GB/T34013-2017) unifies specifications for
power cells, modules, and battery packs to reduce the difficulty
of recycling power batteries. This measure encourages battery
manufacturers to cooperate with comprehensive utilization
enterprises. To ensure safety and control, according to the
principle of recycling after ESS utilization, multilevel and
multipurpose rational use of batteries is of great importance for
reducing energy consumption and improving energy utilization
efficiency.
Figure 20. Proposed “3R strategy and 4H principle” for battery
Several policy documents issued in 2018 accelerate the recycling in the future.
establishment of power battery recycling policy systems to
greatly promote and standardize the power battery recycling.
recycling processes. Simultaneously, redesign of LIBs
The Interim Measures for the Management of Recycling and
packs should allow for disassembly for reuse or recycling.
Utilization of New Energy Vehicle Power Battery clarifies the
The shortage of key resources for LIBs and development
primary responsibility of automobile manufacturers for power
of alternative rechargeable batteries are other solutions to
battery recycling.258 The Interim Provisions on the Management of
this problem. Owing to the complex structure of LIBs,
Traceability of Recycling and Utilization of New Energy Vehicles
most recycling technologies have been designed to
Power Battery require establishment of a platform to monitor the
recover different components. Therefore, a simple
responsibility of each link entity in fulfilling recycling
recycling process is urgently needed to achieve highly
responsibility by collecting information on the whole process
efficient recovery of multiple components. As for cathode
of production, sales, use, scrapping, recycling and utilization of
recycling, the key problem of pyrometallurgical is
power batteries.265 Notice on Pilot Work on Recycling and
reducing the energy consumption and avoiding exhaust
Utilization of Power Battery for Electric Vehicles determines pilot
gas pollution; hydrometallurgical methods require more
areas and enterprises for the power battery recycling, making
rapid and efficient removal of impurities to increase the
that China’s power battery recycling work has entered a large-
purity of the regenerated materials. Recovery of electro-
scale implementation stage.266
lyte and anode materials from the perspective of
environmental protection should also be a focus of future
8. CONCLUSION AND FUTURE PERPECTIVES attention.
Energy and environmental issues are two inevitable problems in ii. Economic aspects: The economic benefits of recycling
human development. Decarbonized electricity and electrifica- processes are fundamental for recycling enterprises to
tion of the transport sector are considered to be the most survive and sustain. On the basis of cost−benefit
promising solutions to solve these problems. LIBs are effective calculations, reducing the cost and increasing the value
energy storage devices for electrified transport and ESS. of products are the main ways to increase economic
Consequently, production of LIBs is increasing every year efficiency. Therefore, simple processing, low-cost, and
together with the popularity of EVs. These trends will lead to high-value-added or high-purity products are desirable.
large volumes of retired LIBs and shortages of Li resources. Additionally, treatment of secondary pollution such as
Many breakthroughs have been made to solve these problems; wastewater, waste gas, and waste residue should be
however, the field of LIB and next-generation rechargeable included in economic analyses. Most importantly, multi-
battery recycling remains challenging. This new comprehensive ple types of rechargeable batteries with different recycling
evaluation standard is based on our previous 3E assessment values should use appropriate recycling technologies to
standard of ‘‘efficiency, economy, environment” with the ensure the greatest possible recycling benefits.
addition of an important safety evaluation factor. It is denoted
by the principle of 4H, namely high-efficiency, high-economic iii. Environmental and safety aspects: Improving the energy
return, high-environmental benefit, and high-safety (Figure 20). efficiency of the manufacturing process, reducing the
To fulfill the ‘‘redesign, reuse, recycle’’ 3R strategy and 4H heavy metal content of electrode materials, and choosing
principle for battery recycling, many issues need to be environmentally friendly binders and electrolytes helps to
considered: reduce the environmental effects of rechargeable
batteries. Given the complex components of rechargeable
i. Technical aspects: In addressing the large number of batteries, recovery processes might be potentially danger-
retired LIBs, safe and efficient automatic disassembly is ous and produce secondary pollution, such as wastewater,
the primary task for avoiding potential hazards in future gas, and residues, which need to be prevented and treated
AJ https://dx.doi.org/10.1021/acs.chemrev.9b00535
to achieve zero emissions of secondary pollution. Authors

Therefore, there is a need for spent battery recycling Ersha Fan − Beijing Key Laboratory of Environmental Science and
plants to be equipped with secondary pollution Engineering, School of Materials Science and Engineering, Beijing
prevention equipment and to develop sound control Institute of Technology, Beijing 100081, China
measures. Some processes that are most likely to cause Li Li − Beijing Key Laboratory of Environmental Science and
secondary pollution include electrolyte recycling and Engineering, School of Materials Science and Engineering, Beijing
treatments, spent battery storage and disassembly, the use Institute of Technology, Beijing 100081, China; Collaborative
of acid and alkali in hydrometallurgical processes, and the Innovation Center of Electric Vehicles in Beijing, Beijing 100081,
production of high-energy and high-pollutant waste gas China
from pyrometallurgy. These aspects should be considered Zhenpo Wang − National Engineering Laboratory for EVs,
during the recovery process. However, control over Beijing Institute of Technology, Beijing 100081, China;
generation of pollution at the source, by exploring less Collaborative Innovation Center of Electric Vehicles in Beijing,
polluting and low-energy recycling technologies, and Beijing 100081, China
replacing toxic agents with nontoxic agents should also be Jiao Lin − Beijing Key Laboratory of Environmental Science and
promoted. Engineering, School of Materials Science and Engineering, Beijing
Institute of Technology, Beijing 100081, China
iv. Data collection: Establishing a comprehensive manage- Yongxin Huang − Beijing Key Laboratory of Environmental
ment platform for battery recycling traceability is Science and Engineering, School of Materials Science and
essential. By collecting battery full life cycle information Engineering, Beijing Institute of Technology, Beijing 100081,
on production, sales, use, retirement, and recycling, it is China
possible to monitor each link in real-time to fulfill its Ying Yao − Beijing Key Laboratory of Environmental Science and
recycling responsibility and organize battery recycling. Engineering, School of Materials Science and Engineering, Beijing
These massive amounts of data can be used as a basis for Institute of Technology, Beijing 100081, China; orcid.org/
retired battery evaluation for secondary use and 0000-0002-0472-0852
evaluation of recycling technology. However, compre-
hensive collection of data on spent batteries will be Complete contact information is available at:
difficult to achieve. Local and national governments, https://pubs.acs.org/10.1021/acs.chemrev.9b00535
enterprises, and individuals should commit to establishing
complete and clear comprehensive utilization industry Author Contributions
and network chains for rechargeable battery recycling. At ∥
Ersha Fan and Li Li contributed equally to this work.
the same time, governments should formulate relevant Notes
standards and specifications in the field of battery
recycling, such as information traceability for battery The authors declare no competing financial interest.
management standards; technical standards for battery
Biographies
disassembly, classification, labeling, storage, and entry of
information; and standards for residual energy detection Ersha Fan is currently a Ph.D. candidate under the supervision of Prof.
and residual value assessment for retired batteries. Li Li at Beijing Institute of Technology University. Her research
We are in a golden age of LIBs and next-generation interests focus on the recycling of spent lithium-ion batteries (LIBs)
rechargeable batteries. Advances in technology will lead to and the synthesis of electrode materials for LIBs.
new techniques for studying rechargeable batteries and Li Li is a professor in Beijing Key Laboratory of Environmental Science
facilitating practical applications of rechargeable batteries in and Engineering, School of Materials Science and Engineering, Beijing
EVs and ESSs. The development of EVs and rechargeable Institute of Technology (BIT), China. Her research interests focus on
batteries has led to a large number of rechargeable batteries electrochemical energy storage and conversion technology and the
entering into the decommissioning stage. Consequently, more recycling technique and life-cycle analysis for spent secondary batteries.
As the principal investigator, Dr. Li successfully hosted the National
scientific exploration is required into the efficiency, security,
Key Program for Basic Research of China, National High Tech 863
economy, and environmental characteristics of rechargeable
project, National Natural Science Foundation, etc. She has authored/
battery development, secondary battery use, and recycling. coauthored over 100 research papers and filed 20 patents and patent
applications in China.
AUTHOR INFORMATION
Zhenpo Wang is a professor in National Engineering Laboratory for
Corresponding Authors EVs, School of Mechanical Engineering, Beijing Institute of
Renjie Chen − Beijing Key Laboratory of Environmental Science Technology (BIT), China. His research interests focus on electric
and Engineering, School of Materials Science and Engineering, vehicle control technology, power battery pack management
Beijing Institute of Technology, Beijing 100081, China; technology, and the recycling technique for spent secondary batteries.
Collaborative Innovation Center of Electric Vehicles in Beijing, As the principal investigator, Dr. Wang successfully hosted the National
Beijing 100081, China; orcid.org/0000-0002-7001-2926; Key Program for Basic Research of China, National High Tech 863
Email: chenrj@bit.edu.cn project, National Natural Science Foundation, etc. He has authored/
Feng Wu − Beijing Key Laboratory of Environmental Science and coauthored over 60 research papers and filed 40 patents and patent
Engineering, School of Materials Science and Engineering, Beijing applications in China.
Institute of Technology, Beijing 100081, China; Collaborative Jiao Lin received her Master’s degree from Beijing Institute of
Innovation Center of Electric Vehicles in Beijing, Beijing 100081, Technology (BIT) in 2019. She is currently a Ph.D. candidate at the
China; Email: wufeng863@bit.edu.cn BIT University. Her research interests focus on the recycling of spent
AK https://dx.doi.org/10.1021/acs.chemrev.9b00535
lithium-ion batteries (LIBs) and the synthesis of electrode materials for (8) Global lithium battery market trends and competitive trends in 2018−
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ABSTRACT: Tremendous eﬀorts are being made to develop electrode materials,

technologies such as electric vehicles, decarbonized electricity, and electrochemical energy

CONTENTS 5.3.3. Material Extraction Technology V

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.chemrev.9b00535

possibilities and diﬃculties of recycling rechargeable batteries

Table 1. Related Policies of EVs in the Following Four Countries

BMW/Vattenfall Household energy storage 26.4 kWh BMW i3 2016

Chem. Rev. XXXX, XXX, XXX−XXX

Table 3. Economic Assessments of Present Recycling Processes

Chem. Rev. XXXX, XXX, XXX−XXX

operation procedures, storage, and management of spent battery

to achieve zero emissions of secondary pollution. Authors

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