Advanced Science - 2017 - Liu - Advanced Energy Storage Devices Basic Principles Analytical Methods and Rational

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Review
Energy Storage www.advancedscience.com
Advanced Energy Storage Devices: Basic Principles,

Analytical Methods, and Rational Materials Design
Jilei Liu, Jin Wang, Chaohe Xu, Hao Jiang,* Chunzhong Li, Lili Zhang,* Jianyi Lin,
and Ze Xiang Shen*
1. Introduction
Tremendous efforts have been dedicated into the development of high-perfor-
mance energy storage devices with nanoscale design and hybrid approaches. Urgent exploitation of renewable and sus-
The boundary between the electrochemical capacitors and batteries becomes tainable energy sources, such as wind and
less distinctive. The same material may display capacitive or battery-like solar energy, has been prompted by envi-
ronmental concerns related to the con-
behavior depending on the electrode design and the charge storage guest
tinuous consumption of nonrenewable
ions. Therefore, the underlying mechanisms and the electrochemical pro- resources and the increasing complexity
cesses occurring upon charge storage may be confusing for researchers who of power distribution systems. Efficient
are new to the field as well as some of the chemists and material scientists usage of these new energy sources is cru-
already in the field. This review provides fundamentals of the similarities and cial concerning their nonconstant power
generation. Hence, a popular strategy is to
differences between electrochemical capacitors and batteries from kinetic and
develop advanced energy storage devices
material point of view. Basic techniques and analysis methods to distinguish for delivering energy on demand.[1–5]
the capacitive and battery-like behavior are discussed. Furthermore, guide- Currently, energy storage systems are
lines for material selection, the state-of-the-art materials, and the electrode available for various large-scale applica-
design rules to advanced electrode are proposed. tions and are classified into four types:
mechanical, chemical, electrical, and elec-
trochemical,[1,2,6–8] as shown in Figure 1.
Mechanical energy storage via pumped hydroelectricity is
Dr. J. Liu, Dr. J. Wang, Prof. Z. X. Shen
Division of Physics and Applied Physics currently the dominant energy storage method. However,
School of Physical and Mathematical Sciences electrochemical energy storage (EES) systems in terms of
Nanyang Technological University electrochemical capacitors (ECs) and batteries have demon-
Singapore 637371, Singapore strated great potential in powering portable electronics and the
E-mail: zexiang@ntu.edu.sg
electrification of the transportation sector due to the advanta-
Dr. C. Xu
College of Aerospace Engineering
geous features of high round-trip efficiency, long cycle life, and
Chongqing University potential to be implemented with various chemistries based on
Chongqing 400044, P. R. China cheap, sustainable and recyclable materials, and low mainte-
Prof. H. Jiang, Prof. C. Li nance cost.[1,2,6] Generally, electric energy is stored in EES in
Key Laboratory for Ultrafine Materials of Ministry of Education two ways: directly via a non-faradaic process or indirectly via
School of Materials Sciences and Engineering a faradaic process.[9] The non-faradaic technologies store elec-
East China University of Science and Technology
130 Meilong Road, Shanghai 200237, P. R. China tricity directly in an electrostatic way. Typically, electric double-
E-mail: jianghao@ecust.edu.cn layer capacitors (EDLCs) are efficient (≈100%) and suitable for
Dr. L. Zhang power management (e.g., frequency regulation), but deliver a
Heterogeneous Catalysis low energy density with limited discharge time.[10] Alternatively,
Institute of Chemical Engineering and Sciences electrical energy can be stored by converting it to available
A*star, 1 Pesek Road, Jurong Island 627833, Singapore
E-mail: zhang_lili@ices.a-star.edu.sg
chemical energy, requiring faradaic oxidization and reduction
Prof. J. Lin
of the electrochemically active reagents, and reversibly release
Energy Research Institute @NTU (ERI@N) the energy on demand. Typical examples of faradaic systems
Nanyang Technological University include pseudocapacitors and various batteries. Ragone plot in
Singapore 639798 Singapore Figure 2a compares the power and energy relationship of var-
The ORCID identification number(s) for the author(s) of this article ious EES systems. Pike Research forecasted that the grid-scale
can be found under https://doi.org/10.1002/advs.201700322. stationary EES system revenues will grow from $1.5 billion in
© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, 2010 to $25.3 billion over the following ten years, with the most
Weinheim. This is an open access article under the terms of the Creative significant growth in EES technologies.[6,11]
Commons Attribution License, which permits use, distribution and re-
While there is significant potential for the application of
production in any medium, provided the original work is properly cited.
EES technologies, their operating performance is still lagging
DOI: 10.1002/advs.201700322 behind the increasingly harsh requirements of industry. One
Adv. Sci. 2018, 5, 1700322 1700322 (1 of 19) © 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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www.advancedsciencenews.com www.advancedscience.com
Jilei Liu received his

Ph.D. degree in Physics
and Applied Physics from
NTU, Singapore, in 2015.
His research interests
include the green produc-
tion of high-quality carbon
allotropes (CNTs, GF, GF/
CNT hybrid films), the
sustainable development of
high-performance electro-
chemical energy storage devices (Li/Na/K-ion batteries,
alkaline rechargeable batteries, asymmetric supercapaci-
tors) for renewable energy storage and delivery, and the
in-depth understanding of fundamental device electro-
chemistry. Ji Lei is a member of International Society of
Electrochemistry and The Electrochemical Society.
Hao Jiang received his

Ph.D. degree in Materials
Science and Engineering
Figure 1. Classification of different types of energy storage technologies from East China University
for stationary applications. of Science and Technology
(ECUST), China, in 2009.
key challenge is the identification of ideal electrode materials He then joined Temasek
that satisfy the requirements of high energy/power densi- Laboratories, Nanyang
ties and long cycle.[12] Strategies such as decreasing the par- Technological University
ticle size,[13,14] controlling the morphology,[15] and producing (NTU) in Singapore, as
hybrid materials[16] have been proposed. Such novel electrode a research scientist from
materials reduce the gap in electrochemical behavior between 2009 to 2011. Now he is a
ECs and batteries, mainly because of the popular trend toward full professor in Key Laboratory for Ultrafine Materials of
increasing the mutual penetration of nanostructured materials Ministry of Education at ECUST, and becomes the winner
(combining the high energy density of batteries with the high of the National Science Fund for Excellent Young Scholars
power density of pseudocapacitors). For example, the same in 2015. His current research interests focus on the design
electrode material may display pseudocapacitive or battery-like and synthesis of novel hierarchical nanomaterials for
behavior depending on its structure, morphology, particle size, energy storage and conversion.
and intercalation ion (i.e., Li+ or Na+). In addition, the fabrica-
tion of hybrid materials that combine two or more electroactive Ze Xiang Shen is a professor
materials in a single-electrode design increases the complexity in the school of Physical
of the electrochemical behavior.[17] Detailed comparisons of and Mathematical Sciences,
EES devices via appropriate measurements and analyses would and the School of Materials
be helpful to avoid any confusion and inappropriate claims in Science and Engineering,
the field of electrochemical energy storage. Moreover, such an NTU, Singapore. He con-
investigation would promote better fundamental understanding currently holds the posi-
and provide basic guidance for material selection and electrode tion of co-director, Centre
design for high-performance energy storage devices. for Disruptive Photonics
In this review, we first introduce fundamental electrochem- Technologies. His research
istry principles and the basic analysis methods used to identify areas include carbon-
capacitive features. Based on these general properties we will related materials, especially
discuss examples of how pseudocapacitive and battery-type graphene. His work involves spectroscopic and theo-
materials are distinguished and classified. We then introduce retical study of few-layer graphene and folded graphene,
the state-of-the-art materials and electrode design strategies graphene-based composites for energy harvesting and
used for high-performance energy storage. Intrinsic pseudo- nanoelectronics, as well as fundamentals on electronic
capacitive materials are identified, extrinsic pseudocapacitive structures, doping, and intercalation. He also works on
materials are discussed, and novel hybrid structures are pro- developing near-field Raman spectroscopy/imaging tech-
posed for high-performance energy storage devices. This review niques and the study of plasmonics structures.
is expected to contribute to a better fundamental understanding
Figure 2. a) Ragone plot comparing the power-energy characteristics and charge/discharge times of different energy storage devices. b) Schematic
diagram comparing the fundamental mechanisms of electrochemical energy storage in double-layer capacitors, pseudocapacitors, and batteries.
Reproduced with permission.[22] Copyright 2016, The Springer Nature.
of the electrochemistry and practical analysis methods for of pseudocapacitors and batteries. The EDL capacitance is
characterizing various nanostructured electrode materials for described as follows[9,10]
advanced electrochemical energy storage technologies.
Q ε rε o A
C dl = = (1)
V d
2. Principle of Energy Storage in ECs
where Cdl is the EDL capacitance of a single electrode, Q is the
EC devices have attracted considerable interest over recent total charge transferred at potential V, εr is the dielectric con-
decades due to their fast charge–discharge rate and long stant of the electrolyte, εo is the dielectric constant of vacuum, d
life span.[18,19] Compared to other energy storage devices, is the charge separation distance, and A is the electrode surface
for example, batteries, ECs have higher power densities and area.
can charge and discharge in a few seconds (Figure 2a).[20] When Cdl is constant for EDLCs, the following equation
Since General Electric released the first patent related to ECs describing the response current I can be derived from
in 1957,[21] these devices have been applied in many fields, Equation (1)
including power capture and supply, power quality applications,
and backup power.[19] dQ dV
I= = C dl (2)
dt dt
2.1. Basics of Double Capacitance and Pseudocapacitance where t is the charge time.
If the applied voltage V varies with time t in a linear way, that
ECs are classified into two types based on their energy storage is, V = V0 + vt (where V0 is the initial voltage and v is the sweep
mechanisms: EDLCs and pseudocapacitors (Figure 2b).[9,23,24] rate (V s−1 or mV s−1)), the relationship can be described as
In EDLCs, energy is stored via electrostatic accumulation of
charges at the electrode–electrolyte interface.[19] In the case I = C dl v (3)
of pseudocapacitors, energy is stored by the electrosorption
and/or reversible redox reactions at or near the surface of the The current responds linearly with the sweep rate, as shown
electrode material, usually a conducting polymer or transition in Equation (3). This translates into a well-defined rectangular
metal oxide.[18,22,24–26] In general, both these mechanisms exist current (I)–voltage (V) plot or cyclic voltammogram for dif-
in a supercapacitor device. ferent sweep rates (Figure 3a). Alternatively, if the capacitor is
charged or discharged under a constant current, the voltage will
increase (charging) or decrease (discharging) with a constant
2.1.1. Charge Storage Mechanism in EDLCs rate, as calculated by Equation (3). Thus, a triangular charge/
discharge curve is expected, as shown in Figure 3b.
The energy storage of EDLCs is via charge adsorption at the sur- Over the past decades, significant progresses have been
face of the electrode without any faradaic reactions.[24,27] During made in fundamental understanding and design of electrode
the charge/discharge processes, the arrangement of the charges materials for energy storage devices. Carbon-based mate-
in the Helmholtz double layer results in a displacement cur- rials, such as activated carbons (ACs),[29,30] carbon nanotubes
rent. Since the materials can respond quickly to the change of (CNTs),[31] and graphene,[32,33] are regarded as EDLC super-
potential and the physical reaction in nature, EDLCs can deliver capacitors, where their electrode surface area and surface
energy quickly, as shown in the Ragone plot in Figure 2a.[23,28] state,[34–36] pore structure and pore size distribution,[29,37,38] and
However, due to the confinement of the electrode surface, the number of carbon layers,[39] are critical parameters. To date,
amount of stored energy is limited and much lower than that great efforts have been made to improve the energy density of
Figure 3. Cyclic voltammograms (top) and galvanostatic charge/discharge curves for different types of electrode materials. a,b) Carbon-based double-
layer supercapacitor. Reproduced with permission.[49] Copyright 2013, Chinese Materials Research Society. c,d) Polyaniline pseudocapacitive electrode.
Reproduced with permission.[50] Copyright 2013, The Royal Society of Chemistry, and e,f) LiFePO4 battery electrode (vs Li). Reproduced with permis-
sion.[51] Copyright 2015, The Royal Society of Chemistry. These series show a wide range of sweep rates and current densities, highlighting the unique
electrochemical features of each material. A transition from (a, b) typical capacitive behavior to (e, f) typical battery behavior has been well illustrated
with (c, d) pseudocapacitive behavior as an intermediate case.
EDLCs, considering matching carbon pore sizes with the elec- When a potential is applied to a metal, an adsorbed mon-
trolyte ion size,[38] oxygen functionalizing the carbon surface[40] olayer will form on the surface due to the reduction of a dif-
or tailoring the oxygen content,[41] modifying carbon with het- ferent metal ion, resulting in a less negative potential than their
eroatom (N, S, F, etc.) doping[42–44] or co-doping,[45,46] adopting equilibrium potential; this process is referred to as UPD.[55,56]
redox active species-based electrolytes,[47] and designing ionic The deposition of Pb on Au is a typical example of UPD.[52,57]
liquids with high working voltage and a wide temperature As the PbAu interaction is stronger than that of PbPb in
range.[48] However, EDLC supercapacitors can still not meet crystalline Pb metal, Pb can deposit onto Au more easily than
the rigid requirement for high-energy density devices due to onto itself. UPD can be applied both to metal deposition and
intrinsic drawbacks, limiting their large-scale application. other adsorbed layers, for example, H from H3O+ or H2O
pseudocapacitance.[58]
The redox system is a typical form of pseudocapacitance,
2.1.2. Transition from Electrophysical Storage where the mechanism involves the adsorption of electroactive
to Pseudocapacitive Storage ions onto the surface or near-surface region of electrode mate-
rials and faradaic reactions occur with charge transfer. Typical
Pseudocapacitance is a faradaic energy storage based on the examples include transition metal oxides (e.g., RuO2[59,60] and
fast redox reaction on the surface or near-surface region of MnO2[61,62]) and conducting polymers generated using electro-
the electrodes, where electrosorption/electrodesorption occurs chemical methods (e.g., polyaniline (PANI),[63,64] polypyrrole,[65,66]
with charge transfer but without any bulk phase transforma- and poly(3,4-ethylenedioxythiophene)[67,68]). Transition metal
tion upon charging/discharging (Figure 2b).[26,52,53] The state of oxides exhibit pseudocapacitance on the bias of fast redox reac-
charge (q) is a function of the electrode potential with the extent tions caused by the intercalation of protons (H+) or alkali metal
of faradaic charge/discharge (Q) passed.[24] The change in Q cations (C+ = Na+, K+, etc.), as described below[69,70]
with respect to the potential gives rise to the derivative, dQ/dV,
which corresponds to the pseudocapacitance (C∅).[26] Unlike MO2 + H+ + e − ↔ MOOH (4)
EDL capacitance, which is associated with potential-dependent
accumulation of electrostatic charge (Figure 3a,b), pseudoca- or
pacitance is faradaic in nature (Figure 3c,d).[24,26,54] In addition,
there are differences between pseudocapacitance and the ideal MO2 + C+ + e − ↔ MOOC (5)
Nernstian process involved in battery-type materials where fara-
daic reactions occur at a constant potential (Figure 3e,f).[54] Upon charging/discharging, no chemical transformation
According to Conway et al., pseudocapacitance can be clas- occurs, but a reversible functionalized molecular layer forms
sified into three types: (i) underpotential deposition (UPD) on the electrode surface due to faradaic reactions. The poten-
(2D), (ii) surface redox system (2D), and (iii) intercalation tial of the electrode has a linear dependence on the charge and
system (quasi-2D), as shown by the schematic diagrams in is proportional to the area of the electrode surface covered by
Figure 4.[24,26] electroactive ions. These features are completely different from
Figure 4. Schematic diagrams of the different faradaic processes that give rise to pseudocapacitance. Here, X is the 2D site occupancy fraction for
underpotential deposition, [OX]/([OX] + [Red]) for redox systems and the occupancy fraction of layer lattice for intercalation systems, respectively.
Reproduced with permission.[22] Copyright 2016, The Springer Nature.
the redox reactions involved in a battery-type electrode, as men- and Tn denotes surface functionalization), are introduced as
tioned previously. unique host materials for intercalation pseudocapacitors.[81,82]
ECPs can store and release charges through redox pro- High-volume pseudocapacitors have been developed through
cesses involving the π-conjugated polymer chains during elec- the intercalation of ions such as Li+, Na+, K+, NH4+, or Al3+
trochemical doping–undoping, as described in the following into Mxene layers. As shown in Equation (7), Ti3C2Tn, a typical
reaction[71–73] Mxene material, shows high volumetric capacitance values due
to changes in the Ti oxidation state during the intercalation/
[ECP] + nX − ↔ (ECP) nX −  + ne −
n+
(6) de-intercalation processes
During the oxidization (p-doping) process, the anionic spe- Ti 3C2Ox (OH)y F2−x −y + δe − + δH+ ↔ Ti 3C2Ox −δ (OH)y+δ F2−x −y (7)
cies X− from the electrolyte are inserted into the polymer back-
bone and are released back into the electrolyte upon reduction. These three pseudocapacitance mechanisms are based on
The embedding and stripping of counter ions enable high different faradaic processes and occur in different types of
specific capacitance values, similar to a battery-type reaction. materials; however, they deliver similar thermodynamic fea-
However, ECPs suffer from volumetric changes during such tures, that is, a logarithmic relationship between the electrode
reactions and poor cycling performance is observed due to poor potential and the extent of charge/discharge, as shown in
mechanical properties of these inherently brittle materials.[73] Figure 4[9,18,24,53]
Hence, many efforts have been made to overcome these draw-
backs. The most desirable and programmable way is to com- RT X
E = E0 + ln (8)
bine carbon materials (e.g., CB,[74] CNTs,[75] or graphene[76]) nF 1 − X
with ECPs to improve the mechanical properties.
Intercalation pseudocapacitance is another faradaic pro- where E is the electrode potential (V), R is the ideal gas constant
cess occurring without a crystallographic phase change and (8.314 J mol−1 K−1), T is the temperature (K), n is the number of
arising when intercalation sorption of the quasi-2D electroac- electrons, F is Faraday’s constant (96 485 C mol−1), and X is the
tive species take place. It differs from the intercalation process occupancy fraction of the surface or lattice layer.
involved in a battery where crystallographic phase transforma- If the electrochemical sorption of electroactive species fol-
tion occurs during the charge transfer processes. Intercalation lows an electrochemical Langmuir isotherm,[52,53] as shown
systems in pseudocapacitors include the intercalation of Li+ in Equation (9), the pseudocapacitance is defined as shown in
ions into hosts such as TiS2,[57,77] MoS2,[78,79] and V6O13[80] or Equation (10),[24] where q* is the charge required for comple-
the intercalation of H into Pd and Pd-Ag alloys.[52,57] Recently, tion of monolayer sorption:
novel 2D materials have been developed. Among them, tran-
sition metal carbides (MXenes) with the chemical formula X  VF 
= k ⋅ exp   (9)
Mn+1XnTn (where M is a transition metal, X is C and/or N, 1− X  RT 
Figure 5. CV profiles of a) ideal double-layer capacitor and b–d) reversible pseudocapacitors with different sweep rates v, where v0 is the critical sweep
rate.[24,83,84] Reproduced with permission.[24] Copyright 1991, The Electrochemical Society.
dX ideally no or only small potential shifts between the anodic and

C∅ = q * ⋅ (10)
cathode peaks under various sweep rates (Figure 5a,b).[18,24]
dV
With the exception of air and vacuum dielectric capacitors,
From Equations (9) and (10), it is identified that the pseu- all ECs have an effective equivalent series resistance (ESR),
docapacitance C∅ is not constant and has a maximum value which results in the polarization effect and deviations from
at X = 0.5. Pseudocapacitors store energy in a similar way ideal capacitive behavior.[24] The presence of the charge transfer
to EDL capacitors (where the stored charge is a continuous resistance in pseudocapacitors imposes kinetic limitations.
function of E), while the main difference is that pseudoca- If the surface faradaic processes involved for pseudocapaci-
pacitance involves faradaic charge transform. Specifically, for tors are modulated by an increasing sweep rate (v), the kinetic
pseudocapacitance, the electrode potential is associated with reversibility is gradually lost.[24] This is manifested by the peak
the conversion of the electroactive material, such as the degree potential, Ep, which remains independent of v until a critical
of utilization of free sites on the surface or within the 2D or sweep rate vo is reached (where the kinetic behavior is radi-
quasi-2D material (ΔG = ΔGθ + RT In(X/(1 − X)). In the case cally different), and then increases with log v.[85] For example,
of most battery electrodes, a certain electrode potential is deter- with an increase in the difference between the cathodic and
mined by the Gibbs free energies of pure, well-defined 3D anodic peak voltage (ΔEa,c) as v > vo, a transition from revers-
phases and usually also the composition and/or concentration ible to irreversible kinetic processes occurs. And cyclic voltam-
of the solution (ΔG = − nFEθ).[4,9] In addition, pseudocapacitors mograms are no longer mirror images of each other (as shown
always show higher rate capability values than batteries bene- in Figure 5c,d).[83,84] However, the kinetic reversibility can be
fiting from the surface/near surface reaction (Figure 2). regained for a pseudocapacitor by lowering the sweep rate,
since no phase change occurs during the charge/discharge pro-
cesses. The presence of a kinetic limitation (characterized by
2.2. Kinetic Electrochemical Features of ECs the vo value) determines the effective charge/discharge rates or
power performance of ECs.
The difference in charge storage mechanisms leads to different The cyclic voltammograms of EDLCs always exhibit a rectan-
kinetic behavior upon the application of (i) potentiodynamic gular shape with no or little deviation upon increasing sweep
sweep and (ii) constant current (galvanostatic charge/discharge rate, while those of pseudocapacitors can be rectangular, with or
curves)[18,24] as shown in Figure 3. These mechanisms will be without cathodic/anodic peaks (or wide bumps), depending on
discussed in the following sections in more detail. the type of electrode material. Conductive polymers including
polyaniline,[86] polypyrrole, and PEDOT,[87] and transition metal
oxides involving MoO3,[88] V2O5,[89] T-Nb2O5,[90] tend to have
2.2.1. Potentiodynamic Sweep Cyclic Voltammetry (CV) broad redox peaks (Figure 6c). Hydrous RuO2[91,92] (Figure 6a)
and MnO2[93] (Figure 6b) have been extensively investigated and
During CV testing, an ideal capacitive system shows sym- exhibit nearly ideal rectangular CV curves without distinct redox
metric cyclic voltammograms at slow sweep rates, and there is peaks in aqueous electrolytes. Recently, cyclic voltammograms
Figure 6. Typical CV profiles of: a) hydrous RuO2. Reproduced with permission.[92] Copyright 2005, American Chemical Society. b) MnO2. Reproduced
with permission.[93] Copyright 2014, ESG. c) Polyaniline (PANI). Reproduced with permission.[95] Copyright 2014, Elsevier Ltd. d) Mxene Ti3C2Tx with
different sweep rates. Reproduced with permission.[82] Copyright 2014, Nature Publishing Group.
of Ti3C2Tn Mxene were found to have a rectangular shape in than that of the EDL mechanism alone (Figure 7a). Thus, the
sulfuric acid, resulting from the continuous change in the relative contribution of EDL capacitance and pseudocapaci-
titanium oxidation state during charge/discharge processes tance can be estimated from CV results. Only a small fraction
(Figure 6d).[82,94] The CVs of these electrode materials demon- (≈10%) of the total charge results from EDL capacitance, while
strate that the reversible faradaic reactions can exhibit similar the majority is related to the surface confined faradaic charge
electrochemical behavior compared to EDL capacitors. Hence, transfer process. This is further confirmed by the broad redox
it is rather difficult to differentiate these two charge storage peaks in the CV curves (Figure 7b), which is characteristic of a
mechanisms from each other, especially for electrode materials surface-confined charge transfer process.[80] However, it must
that possess both EDL and pseudocapacitive mechanisms. To be emphasized that the experimental method discussed here
date, great efforts have been made to distinguish and estimate has many limitations, including the types and morphology of
the contribution from these two surface-controlled processes. the electrodes. Hence, this method can only provide a rough
Dunn and co-workers[96] demonstrated that CV can be used estimation.
to estimate the contributions from the two charge storage
mechanisms mentioned above through appropriate experi-
mental design. Mesoporous Nb2O5 with crystallographically 2.2.2. Constant Current Charge/Discharge Curves
orientated layered nanocrystalline walls shows intercalation
pseudocapacitance, because guest ions can be easily interca- The profile of the potential versus capacitance for an EDL
lated into the layers due to the weak van der Waal force between capacitor is a well-defined linear shape, as described by
them. When such crystalline mesoporous Nb2O5 is used as Equations (2) and (3) and illustrated in Figure 3b. For pseu-
an electrode, the charge storage mechanism can be altered docapacitors, the electrode potential associated with the elec-
by changing the electrolyte (e.g., the guest cations). When trosorbed species is a continuous logarithmic function over the
tetrabutylammonium (TBA+) perchlorate carbonate is added to extent of sorption (Equation (8)), differs from the linear behavior
the electrolyte, the charge storage changes to the EDL mech- of the EDL capacitor. In a constant current charge/discharge
anism only, according to the CV curve shown in Figure 7a. process, this translates into smooth charge/discharge profiles
Since the bulky TBA+ cannot quickly intercalate into the lay- without pronounced plateaus (Figure 3d). In contrast, bat-
ered Nb2O5. However, both EDL and intercalation pseudoca- tery electrodes always deliver distinct charge/discharge poten-
pacitance contribute to the total charge storage in the LiClO4 tial plateaus in potential versus capacity profiles (Figure 3f),
electrolyte. And a much larger response current is identified accompanying the phase transformations.
Figure 7. a) Cyclic voltammetry curves of amorphous and crystalline mesoporous T-Nb2O5 films in lithium (Li+) and tetrabutylammonium (TBA+)
electrolytes at a sweep rate of 10 mV s−1. b) Potential-dependent capacitance calculated from CV curves at sweep rate of 2 and 50 mV s−1. Reproduced
with permission.[96] Copyright 2010, American Chemical Society.
3. Quantifying the Capacitive Properties related to the slow diffusion-controlled process (idiff) and the
current required to charge the double layer at the electrolyte
Electrochemical analysis of different kinetic responses promotes interface or to initiate fast faradaic reactions on the exposed
better understanding of the charge/discharge mechanism, and electrode surface (icap).[102] An empirical description of this is
provides basic guidance for the identification and design of high-
performance electrode materials for advanced energy storage i ( v ) = icap + idiff = av b (11)
devices. We summarize this analysis into three main approaches
for distinguishing surface or bulk charge storage behavior and log i ( v ) = log a + b log v (12)
pseudocapacitive or battery-type electrode materials in a quan-
titative way: (i) investigating difference of the redox (anodic (a) where both a and b are adjustable parameters.[101,103–105] Param-
and cathodic (c)) peak potentials (ΔEa,c), (ii) establishing the rela- eter b is determined from the slope of the linear plot of log i
tionship between the response current (i) and the sweep rate (v), versus log v and is used to provide kinetic information about
and (iii) quantifying the relative contribution (%) of the capaci- the electrochemical reactions (Equation (11)). There are gener-
tive and diffusion-limited processes. These three methods are ally two well-defined conditions, b = 0.5 and b = 1 (Figure 9).
described in more detail in the following sections. A b value of 1 signifies contributions from fast near-sur-
face activities, such as the fast surface redox reactions and
charging/discharging the EDLCs. Thus, i (v) = icap = av, and
3.1. Redox Peak Difference (ΔEa,c) the response peak current varies linearly with the sweep rate.
While a b value of 0.5 represents the slow semi-infinite diffu-
In CV measurements, the difference between the anodic and sion-controlled faradaic processes that occur in the bulk, such
cathodic peak positions, ΔEa,c, and the voltage shift of the anodic as battery-type processes.[100,101,103,104] Therefore, by estab-
and cathodic peaks with changing v, generally define the level lishing the relationship between the peak current response
of the reversibility of the electrochemical reactions.[97–99] Pseu- and the sweep rate to estimate the value of b, the material type
docapacitors have good reversibility and hence, ΔEa,c is gener- (pseudocapacitive or battery) can be identified and surface-con-
ally very small for these materials (Figures 3c and 8a,b) and trolled processes (such as in EDLCs and pseudocapacitors) can
remains constant over a wide range of v values until the critical be differentiated from diffusion-controlled processes (i.e., in
sweep rate is reached (as described in Section 2.2.1).[24] On the battery-type electrodes). For example, b ≈ 1.0 was determined
other hand, a large ΔEa,c is generally observed for battery-type for the pseudocapacitive material, Nb2O5, (Figure 10a) based
materials that undergo crystallographic phase transformation on Equation (11),[100] whereas a typical battery-type material,
during the electrochemical processes, even at a very low sweep LiFePO4, showed a b value ≈ 0.5 (Figure 10b),[101] over a wide
rate (Figures 3e and 8c,d).[18,23] Typically, ΔEa,c increases with range of sweep rates.
increasing v, resulting in a poor rate performance of the battery The range of b values from 0.5 to 1.0 indicates a “transition”
(Figure 2a). Therefore, broad redox peaks in CV data can indi- area between pseudocapacitive materials and battery-type mate-
cate pseudocapacitive behavior when ΔEa,c is small or remains rials, though a clear boundary is not easy to define. Generally,
constant over a wide range of sweep rates (Figure 8).[18,23] the smaller the b value is, the larger the contribution from dif-
fusion-controlled intercalation processes, while the capacitive
3.2. Relationship between the Response Current and Sweep Rate contribution increases with increasing b value. Typical examples
include the insertion of Li+ into TiO2 films (Figure 10c),[103,106,107]
In CV measurements, the total current measured under a Na+ intercalation into TiO2/graphene nanocomposites,[108] and
potential sweep rate can be interpreted as the sum of the current Li+/Na+ reaction with Li4Ti5O12 (Figure 10d).[109] It was found
Figure 8. Typical CV curves of a) pseudocapacitive material and c) battery-type material at different sweep rates, v1 < v2 < v3. Note that v3 < v0 for a
pseudocapacitor and ΔEa,c increases with increasing v for the battery. Typical experimental data for b) T-Nb2O5. Reproduced with permission.[100] Copy-
right 2013, Nature Publishing Group. d) LiFePO4. Reproduced with permission.[101] Copyright 2011, The Electrochemical Society.
that the b value was strongly dependent on the potential, sweep capacitive contribution. The presence of a critical sweep
rate, and charge storage mechanism, in addition to the mate- rate, as discussed in Section 2.2.1, results in a change in
rial type. For example, a b value of 0.55 at the cathodic peak b value with the sweep rate. As illustrated in Figure 10a, the
potential of 1.70 V was calculated for anatase TiO2 films, b value of Nb2O5 remains around 1 up to 50 mV s−1, and then
indicating that the Li+ intercalation reaction dominated the decreases when the sweep rate increases further, indicating the
current.[103] Away from the peak potential, b increased to kinetics transition from surface-controlled behavior to semi-
0.8–1.0, suggesting that the current primarily stemmed from infinite linear diffusion.[100] Similar phenomenon has also
observed in other electrode materials.[108] In addition, different
charge storage mechanisms also result in different b values
(Figure 10d).[109] For Li+ storage in Li4Ti5O12,[109] b values in the
range of 0.55–0.65, close to 0.5, were observed, indicating that
the charge storage primarily resulted from diffusion-controlled
intercalation processes with well-defined redox peaks and a dis-
tinct charge/discharge plateau. While for the Na+ storage case,
the b values were in the range of 0.7–0.8,[109] higher than that
of Li+ storage. This suggests a higher capacitive contribution
as a result of the larger ionic size of Na+ than that of Li+. This
difference is also manifested in broader CV peaks and a poorly
defined discharge plateau for Na+ storage compared with Li+
storage.
The b value can be used to provide guidance for the practical
design of high-performance electrode candidate materials. For
example, the b value could (i) act as an indicator for differenti-
ating pseudocapacitive from battery-type materials, and (ii) pro-
vide more kinetic information about electrochemical reactions
Figure 9. Power law dependence of the peak current on sweep rate (from
Equation (12)) for capacitive materials (b = 1.0) and typical battery-type in terms of charge storage types at different potential/sweep
materials (b = 0.5). The “transition” area between capacitive and battery- rates and charge storage mechanisms for different ion interca-
type materials area is located in the range of b = 0.5–1.0. lation batteries.
Figure 10. The dependence of parameter b on: a) electrode material types pseudocapacitive T-Nb2O5. Reproduced with permission.[100] Copyright
2013, Nature Publication Group. b) Battery-type LiFePO4. Reproduced with permission.[101] Copyright 2011, The Electrochemical Society. c) Potential
(10 nm TiO2 film). Reproduced with permission.[103] Copyright 2007, American Chemical Society. d) Charge storage mechanism (Li+ and Na+ reactions
in Li4Ti5O12). Reproduced with permission.[109] Copyright 2014, American Chemical Society. The inset in (c) shows the good linear dependence of the
current on the sweep rate (based on Equation (12)) at 1.60 V (b = 1.0) and cathodic peak 1.70 V (b = 0.55). The inset in (d) shows the good linear
dependence of the current on the sweep rate (based on Equation (12)) measured at the cathodic peak near a potential of 0.9 V for the Na+ storage
case and 1.54 V for Li+ storage case.
3.3. Differentiating Capacitive Effect from differentiate the current contribution from the capacitive effect
Diffusion-Controlled Process (k1v) from diffusion-controlled intercalation processes (k2v1/2).
As shown in Figure 11a, the surface-dominant capacity was
Based on the discussion of parameter b in Section 3.2, quan- estimated to be around 88 F g−1 for a MnO2/Au (shell–core)
titatively distinguishing between capacitive processes and hierarchical nanostructure at a sweep rate of 5 mV s−1, and
diffusion-controlled intercalation processes is therefore highly this value was nearly constant over a wide range of sweep rates
desirable for a better understanding of the underlying charge (Figure 11a2,a3). The diffusion-controlled insertion capacity
storage mechanism to aid materials selection and device design. was found to be sweep rate dependent, with the surface/bulk
When the process is controlled by surface-dominant charge ratio increasing gradually.[111]
reactions, the response current varies linearly with v Another method used to differentiate capacitive and dif-
(i.e., di/dv = constant = capacitance). If the process is controlled fusion-controlled processes is by establishing a relationship
by semi-infinite diffusion, the response current varies linearly between the total stored charge and the sweep rate, as devel-
with v1/2 (i.e., di/dv1/2 = constant).[102,110] Thus, a general expres- oped by Ardizzone et al.[113] The total charge q* contains a
sion taking into account all possible cases is[102,110] capacitive contribution qs* (proportional to v) and a diffusion-
controlled contribution qd*(proportional to v1/2)
i (V ) = icap + idiff = k1v + k2v 1/2 (13)
q * ( v ) = qs * + qd* (15)
or The qs* value corresponding to surface-dominant processes
1 1 is obtained at an infinite potential sweep rate (v → ∞), where
i (V ) /v = k1 v + k2
2 2 (14)
q * → qs * (16)
Using Equation (14), the constants k1 and k2 can be evaluated
from the slope and intercept, respectively, of a linear plot of The maximum charge density (qm*) is obtained when
i(V)/v1/2 versus v1/2. Consequently, it is possible to quantitatively v → 0 and
Figure 11. Two different methods for deconvoluting surface (∝v) and bulk charge (v1/2): a1–a3) I ∝ v or v1/2 and b1–b3) q ∝ v1/2 or v−1/2. CV curves
at (a1) 5 and (a2) 100 mV s−1 for MnO2 (74 nm shell)-Au (core) hierarchical structure. (a3) Dependence of surface/bulk charge ratio on sweep rate.
Reproduced with permission.[111] Copyright 2012, American Chemical Society. (b1) Gravimetric capacity versus v−1/2 and (b2) inverse gravimetric
capacity versus v1/2 for V2O5/Ru nanotube arrays. The intercept value in (b1) represents the surface charge (∝v). The inverse of the intercept in (b2) is
the total charge. (b3) Surface/bulk charge ratio for V2O5/planar Ru and V2O5/Ru nanotube array hybrids. Reproduced with permission.[112] Copyright
2014, Nature Publication Group.
q * → qm* (17) Therefore, the contributions from the capacitive and the
semi-diffusion controlled processes can be estimated. A typ-
In particular, q* is expected to be limited by v−1/2 if semi- ical example is the electrochemical behavior of V2O5 coated
infinite linear diffusion is involved, whereas capacitive contri- on Au tube arrays.[112] The surface-dominant and total charges
butions are independent of the sweep rate; thus, Equation (15) were estimated to be 156.1 mA h g−1 from a C versus v−1/2
can be expressed as follows plot (Figure 11b1) and 168.4 mA h g−1 from a 1/C versus v1/2
plot (Figure 11b2), respectively. Moreover, the bulk charge can
q * ( v ) = qv → ∞* + qd * = qv → ∞* + const ( v −1/2 )
*
(18) be efficiently increased via a 3D current collector design, as
illustrated in Figure 11b3. This opens a new opportunity for
where the minimum qs* value is determined from the extrapo- achieving high power/energy density electrode materials for
lation of a linear plot of q* versus v−1/2 to v−1/2 = 0. Generally, advanced energy storage devices.
q* decreases as v increases because of diffusion limitations.[113]
Since q* increases linearly with v−1/2, it is reasonable to expect
that 1/q*(v) decreases linearly with v1/2 4. Optimizing Pseudocapacitive Electrode Design
1/q * ( v ) = 1/qm* + const ( v )
1/2 *
(19) The methods discussed in Section 3 for quantitatively differ-
entiating the two charge storage mechanisms can be used to
where qm* is the maximum total charge. Extrapolation of identify high-performance intrinsic electrodes, explore extrinsic
a linear plot of 1/q*(v) versus v1/2 to v1/2 = 0 gives the basic electrode behavior, and design novel hybrid electrodes.
amount of the maximum total charge qm*. Consequently, Materials including mesoporous α-MoO3,[114] TiO2,[103,108,115]
the difference between the total charge (qm*) and the surface Nb2O5,[100] hierarchical MnO2,[116] and Li4Ti5O12[109] have
charge (qv → ∞*) gives the charge associated with the diffusion- been well described using Equations (11) and (12). It is
controlled processes not surprising that the contribution from the two different
processes (capacitive and diffusion-controlled) is strongly
qd* = qm* − qv → ∞* (20) dependent on the structure, crystallinity, and morphology
of the electrode materials,[96,103,114,116] type of electrolyte,[96,116] 4.1.1. TiO2 (B) and Hydrogen Titanates
sweep rate,[116] and charge storage mechanism.[109] Gener-
ally, the capacitive contribution dominates the total current TiO2 (B) is a metastable modification of titanium dioxide with
response or charge storage for EDL and pseudocapacitive the monoclinic structure (space group C2/m; lattice para
electrodes. Therefore, the contribution ratio of the capaci- meters a = 1.21787 nm, b = 0.37412 nm, c = 0.65249 nm, and
tive versus diffusion-limited process may be another effective β = 107.054°) that is characterized by two edge-sharing TiO6
indicator for differentiating pseudocapacitive materials from octahedra linked to a neighboring pair of octahedra by their
battery-type candidates. corners.[106] This material has a low density (3.64–3.76 g cm−3)
and an open structure, which is particularly suitable for pseu-
docapacitive energy storage.[106,126] The pseudocapacitive
4.1. Intrinsic Pseudocapacitive Materials behavior of TiO2 (B) is characterized by a dominant pseudoca-
pacitive faradaic process via Li+ intercalation. Two pairs of redox
Any electrode material exhibiting linear or approximately peaks located at 1.5 and 1.6 V have been detected in the CV
linear charge/discharge curves without a pronounced voltage curve, accompanying the insertion of Li+ into the TiO2 (B) lat-
plateau and delivering broad and nearly overlapped redox tice.[107] Note that these potentials are lower than that for Li+
couple peaks in CV curves, can be regarded as a pseudoca- intercalation into anatase TiO2 (≈1.70 V) and the redox peaks
pacitive material. Pseudocapacitive behavior can be intrinsic are broader, indicating that a different charge storage mecha-
or extrinsic, depending on the nature of the electrode mate- nism is involved. A linear relationship between the peak cur-
rial and materials engineering undertaken. Intrinsic pseu- rent and sweep rate was observed for TiO2 (B), verifying that
docapacitive materials possess typical characteristics of the accommodation of Li into the TiO2 (B) is dominated by the
capacitive charge storage, regardless of their crystalline prop- capacitive effect. The capacitive contribution was calculated to
erties, morphology, or particle size. Typical intrinsic pseu- be 68% of the total charge for TiO2 (B) (Figure 12a), two times
docapacitive materials include MnO2,[70,117,118] RuO2,[119,120] that of anatase TiO2 (34%, Figure 12d), in spite of the former
and various conducting polymers such as polypyrrole,[121,122] having a surface area three times smaller than the latter.[107]
polyaniline,[64,123] and PEDOT.[124,125] In addition, other pseu- The total stored charge was 625 C g−1 for pure TiO2 (B) at a
docapacitive materials, such as TiO2 (B), α-MoO3, T-Nb2O5,[100] sweep rate of 0.5 mV s−1, which was 27% higher than that for
and Li4Ti5O12,[109] have been identified based on the quantita- anatase (Figure 12d). The pseudocapacitive behavior of TiO2 (B)
tive differentiation of the capacitive effect from the diffusion- is ascribed to the open structure allowing fast Li+ transport in
controlled process. the bulk TiO2 (B) lattice along the b-axis.
Figure 12. The dependence of intrinsic pseudocapacitive behavior on: crystal structure a) TiO2 (B) and d) anatase TiO2. Reproduced with permis-
sion.[107] Copyright 2014, Elsevier Ltd. b) a-MoO3 and e) amorphous MoO3. Reproduced with permission.[114] Copyright 2010, Nature Publication
Group. and charge storage mechanism c) Na+ storage and f) Li+ storage. Reproduced with permission.[109] Copyright 2014. American Chemical Society.
Hydrogen titanates, primarily H2Ti3O7, have also shown 4.1.3. Li4Ti5O12

pseudocapacitive behavior, characterized by broad redox
peaks and the liner dependence of the peak current on Spinel-type Li4Ti5O12 (LTO), is a promising “zero-strain” anode
the sweep rate.[126–130] Its layered structure consisting of material for lithium-ion battery that experiences a two-phase
zigzag ribbons of edge-sharing TiO6 octahedra provides reaction (Li4Ti5O12/Li7Ti5O12) and shows a well-defined voltage
an open-layered framework to facilitate Li+ insertion. plateau (1.55 V vs Li/Li+).[138,139] It was found that sodium ions
Note that hydrogen titanates undergo consecutive phase can also be reversibly inserted/extracted from the Li4Ti5O12
changes with increasing temperature: TiO2 (B) at 400 °C, lattice, in spite of Na+ having a larger ionic radius (0.102 nm)
anatase at 700 °C, and rutile at 1000 °C.[131] The capacitive than that of Li+ (0.076 nm).[140,141] In contrast to the two-phase
effect of hydrogen titanates is therefore dependent on the reaction in the Li+ intercalation/de-intercalation process, a
annealing temperature and resulting morphology.[132–134] A three-phase reaction (2Li4Ti5O12 + 6Na+ + 6e− ↔ Li7Ti5O12 +
transition from pseudocapacitive behavior of the protonated Na6LiTi5O12) is observed during Na+ intercalation.[141] This dif-
titanate to coexisting pseudocapacitive and diffusion-limited ferent ion charge storage mechanism is also characterized by
behavior of the TiO2 (B) and anatase TiO2 mixture, to the the pseudocapacitive behavior for Na+ storage in Li4Ti5O12 in
diffusion-limited behavior of anatase TiO2 has been well terms of broad redox peaks with small peak separation in CV
studied.[107,133] curves (Figure 12c) and indistinct voltage plateaus in charge/
discharge curves. A capacitive contribution of 51% of the total
charge for Na+ storage was observed, which is two times higher
4.1.2. Orthorhombic MoO3 and Nb2O5 than that for Li+ storage (24%, Figure 12f).[109] The pseudoca-
pacitive behavior of Na+ storage in Li4Ti5O12 depends on the
Orthorhombic MoO3 (α-phase) is another promising pseudo- particle size[142] and film thickness.[109]
capacitor electrode material with an advantageous unique lay- Li4Ti5O12 is a typical battery-type material for Li+ storage, but
ered structure along the [010] direction. The double layers of pseudocapacitive for Na+ storage. Therefore, Li4Ti5O12 exhibits
the MoO6 octahedra are bonded by covalent forces in the[100] intrinsic intercalation pseudocapacitive behavior in nonaqueous
and [001] directions and by Van der Waals forces in the [010] electrolytes. Traditional battery-type materials for Li+ storage
direction.[88,135] The weakly bonded interlayers are particu- can be pseudocapacitive when different guest ion intercalation
larly desirable for ion intercalation and transport, and result processes take place in different electrochemical systems. This
in pseudocapacitance behavior.[136] The corresponding charge is of particular interest for designing high-power energy storage
storage in MoO3 occurs due to (i) redox pseudocapacitance devices based on traditional high-energy density materials via
arising from charge-transfer processes across the interface and introducing different guest ion intercalation reactions.
(ii) intercalation pseudocapacitance resulting from ion inter-
calation into van der Waals gaps.[136] The pseudocapacitive
behavior is strongly dependent on the crystalline structure. 4.1.4. MXenes
Dunn and co-workers[114] found that the capacitive contribu-
tion could be improved significantly for mesoporous α-MoO3 MXenes, a new class of 2D stacked materials, are emerging as
(Figure 12b, 70% of the total charge storage) compared to promising candidates for electrodes in electrochemical energy
amorphous materials (Figure 12e, 35%). The capacitive charge storage applications, such as supercapacitors and batteries,
storage was 450 C g−1 for the crystalline mesoporous film, due to their good conductivity and a broad range of chemis-
three times that of amorphous films (150 C g−1). Moreover, tries.[81,143,144] MXenes are produced by the selective etching
the crystalline films delivered higher total charge storage and of the A-group (generally group IIIA and IVA elements) layers
a faster charging/discharging rate than the amorphous films. from the ternary transition metal carbide (MAX phases, e.g.,
This is attributed to the extra Li+ intercalation pseudocapaci- Ti3AlC2, Ti2AlC, and Ta4AlC3) via wet chemistry routes.[82,145,146]
tance in mesoporous α-MoO3 films due to the iso-oriented MXenes combine the metallic conductivity of transition metal
crystal structure with preferred intercalation planes.[114] carbides with the hydrophilic nature of their hydroxyl or
Dunn and co-workers[100] also discovered that Li ions interca- oxygen-terminated surface. These features are of great interest
lation into T-Nb2O5 possess similar trend with α-MoO3. The for supercapacitor applications. An impressive high volumetric
kinetics of charge storage is also influenced significantly by capacitance (900 F cm−3, comparable with hydrated RuO2)
crystallization.[137] At charging time of only 12 s, the capacity was demonstrated in aqueous electrolytes.[82,147] In situ X-ray
is ≈450 C g−1, and achieves a consistent value of 560 C g−1 absorption spectroscopy (XAS) revealed continuous changes in
as time increases to 2 min; thus, over 80% of the capacity is the Ti oxidization state during charge/discharge cycling.[94] Var-
accessed within 12 s, indicating the ultrafast kinetic response. iations in the distance between the Ti3C2Tx layers (c-axis) due to
The reason is that the mostly empty octahedral sites between cation insertion/de-insertion was estimated to be <5% using in
(001) planes provide natural tunnels for fast diffusion kinetics situ X-ray diffraction, and no phase changes were detected.[81]
in the a-b plane. These results demonstrate how improved It seemed that the capacitive charge storage resulting from
pseudocapacitance can be achieved via the design of unique cationic intercalation/de-intercalation occurred so rapidly that
iso-oriented crystalline mesoporous structures. Hence, gaining it resembled 2D ion adsorption at solid–liquid interfaces.[144,148]
insight into the charge storage mechanisms in different crys- Surface capacitive effects, either electrostatic or pseudocapaci-
talline structure is another effective method for selecting high- tive, dominate charge storage in these materials.[82,144] These
performance electrode materials. findings validate the intrinsic pseudocapacitive nature of
Figure 13. Dependence of the extrinsic pseudocapacitive behavior on crystallite size for a) LiCoO2. Reproduced with permission.[152] Copyright 2007,
American Chemical Society. b) Anatase TiO2. Reproduced with permission.[103] Copyright 2007, American Chemical Society.
MXenes, expand the family of pseudocapacitive materials, and discharge plateau region (the capacity from the inner layers)
provide new insights for designing high-performance electrode decreased gradually and capacitor behavior (the capacity from
materials. the intercalation of Li+ ions into the surface layers) became
more dominant with decreasing crystallite size (Figure 13a).[152]
In particular, a nearly linear discharge curve was observed
4.2. Extrinsic Pseudocapacitive Materials when the particle size reduced to 6 nm, verifying the transition
from battery-type to pseudocapacitive behavior.
Nanostructured materials for EES offer the unique opportunity Similar trends have also been observed for anatase TiO2,
of tailoring the energy and power density and enabling opera- which is another typical battery-type material with a Li+ inser-
tion in the intermediate stage between battery and EC behavior. tion potential plateau at about 1.75 V (Figure 13b).[103,153] The
The optimization of traditional battery-type electrode materials constant-voltage region (indicated by the arrows on the figure)
on the nanoscale has yet to be realized, but it is an exciting that represents a two-phase reaction during the Li+ inser-
direction for increasing their power density because of the tion was much shorter for 7 nm particles (x ≈ 0.15) than that
short ion and electron transport paths.[149] However, the elec- of 30 nm particles (x ≈ 0.35), where x is the Li content in
trochemical responses of traditional battery-type electrodes are LixTiO2.[103] The transition from battery-type to pseudocapacitive
strongly dependent on the particle size and morphology of the behavior is exhibited by a gradual increase in the capacitive con-
electrode material. tribution and a decrease in the peak potential difference (ΔEa,c)
One typical example is LiCoO2, which is a commercial with decreasing particle size. The capacitive contributions were
cathode material for lithium-ion batteries. The bulk LiCoO2 15, 35, and 55% of the total Li+ storage for 30, 10, and 7 nm
exhibits a well-defined discharge plateau at about 3.9 V and particle sizes, respectively.[103] It is clear that capacitive behavior
well-separated redox peaks in CV curves.[150,151] However, the becomes dominant with decreasing crystallite size.
The typical well-defined flat discharge curve of a bulk mate- The second approach focuses on enhancing the electrochemical
rial changes to a sloped curve for nanostructured materials. performance by maximizing the coupling effects of their indi-
This is due to the emergence of extrinsic faradaic reactions vidual components. For the sake of simplicity, the components
on the surface or near-surface region that replace diffusion- of a hybrid electrode are classified as a conductive part (i.e., var-
controlled lithium ion interactions when a battery-type material ious carbon allotropes, metals) and an electrochemically active
is engineered to be nanosized (with a large surface area and part (i.e., pseudocapacitive and battery-type parts).
short ion diffusion distance). Therefore, a superior rate perfor-
mance has been reported for nanocrystals compared to bulk
battery-type materials. Nanosized battery-type materials, such 4.3.1. Binary Hybrids
as V2O5[104] and CeO2,[154] also show extrinsic pseudocapaci-
tive behavior. Materials that exhibit pseudocapacitive behavior The design of hybrid materials, which combine electroactive
on the nanoscale but battery-type behavior in the bulk state are and conducting components in a single electrode, can offset the
therefore denoted as extrinsic pseudocapacitive materials.[18,23] slow charge-transfer kinetics originating from the low electrical
conductivity of the electroactive materials. For example, a V2O5
nanowire/CNT hybrid (sample I, Figure 14a) exhibits enhanced
4.3. Hybrid Materials pseudocapacitive behavior in terms of the specific capaci-
tance and the rate capability compared to pure V2O5 nano
It should be noted that most of the faradaic electrodes that can wires (sample II, Figure 14a) in NaClO4/propylene carbonate
provide surface redox capacitance or ion intercalation show (PC).[155] This better performance was due to the high electrical
poor electronic conductivity. The rational design of electrode conductivity (≈3.0 S cm−1) and the hierarchical porosity of the
materials with fast charge-transfer kinetics in the surface or intertwined networks.[155] In particular, when pure V2O5 nano
bulk is therefore highly desirable. There are several ways to wires were used as the electrode, the total charge came mainly
achieve this, such as decreasing the size or producing a hybrid from the diffusion-controlled process. In the case of the V2O5/
with highly conductive materials. The first approach involves CNT nanocomposite, the capacitive contribution dominated
engineering nanoscale electroactive materials with different the total charge storage at all sweep rates, indicating that most
morphologies (nanoparticles, rods, sheets, branches, etc.) to of the Na+ intercalation sites were available in V2O5 within the
shorten the ion diffusion length (as discussed in Section 4.2). nanocomposite. Moreover, a decrease in total stored charge
Figure 14. Characterization results of binary hybrids. The dependence of capacitive charge and diffusion-controlled charge on the hybrid material a) I is
V2O5/CNT and II is V2O5. Reproduced with permission.[155] Copyright 2012, American Chemical Society. b) V2O5/CNT hybrids with different V2O5 mass
loadings. Reproduced with permission.[104] Copyright 2011, American Chemical Society. And electrolyte type c1) aqueous 1 m LiClO4 and c2) organic
acetonitrile 1 m LiClO4. Reproduced with permission.[116] Copyright 2013, American Chemical Society.
and a transition from capacitive to battery-type behavior was were significantly increased by around 20 and 45%, by 3D
observed with increasing V2O5 fraction in the V2O5/CNT com- conductive wrapping of MnO2/graphene nanostructures with
posites (Figure 14b),[104] resulting from a decrease in overall CNTs and PEDOT-PSS, respectively.[164] This ternary design
surface area and degradation in electrical conductivity. Similar takes advantage of the unique properties of each component,
results were observed for MnO2/Au (shell/core) nanowires with resulting in hybrid composites with high specific capacitance,
different MnO2 thicknesses.[111] Consequently, the design of good rate capability, and long cycle life. Such a strategy high-
high-performance hybrid electrodes with the optimum combi- lights a promising direction for optimizing pseudocapacitive
nation of capacitive and diffusion-controlled charge storage is materials that achieve high energy density and can be inte-
possible via the optimization of mass loading or thickness of grated into high-performance energy storage devices.
the electroactive materials in the hybrid electrode.
Another hybridization approach for optimizing the electrode
design, combining two electroactive constituents to form a 5. Conclusions and Future Perspectives
hierarchical structure in a single electrode, has also been dem-
onstrated.[116] This is equivalent to the parallel combination The full potential of nanostructured capacitive materials, espe-
of faradaic materials, thus increasing the total stored charge. cially extrinsic pseudocapacitive materials, and hybrid elec-
For example, a hierarchical structure consisting of individual trodes has not yet been realized. The performance, in terms of
MnO2 nanowires surrounded by a conformal layer of MnO2 the capacitance, rate capability, and cycle stability, needs to be
nanofibrils showed enhanced area-specific capacitance com- further improved and a proper balance needs to be considered.
pared to bare MnO2 nanowires in both aqueous and organic However, some fundamental criteria for identifying poten-
electrolytes, as shown in Figure 14c1,c2.[116] The increase in tial high-performance pseudocapacitive electrode materials
capacitive charge storage dominated the increase in total capac- have been proposed, along with strategies for hybrid electrode
itance in the aqueous electrolyte. Meanwhile, the increase in design. Intrinsic and extrinsic pseudocapacitive materials have
capacitance using the organic electrolyte mainly resulted from been identified from both thermodynamic and kinetic point of
the increase in diffusion-controlled charge storage. The dif- view. Advanced approaches, aiming at introducing more elec-
ferent charge storage mechanism was attributed to the proton trochemically active sites and shortening the transport path for
adsorption behavior in water that mitigates the lithium inter- electrons and diffusion length for ions, have been discussed.
calation mechanism. A synergetic effect was also identified in This is achieved through the selection of an appropriate pseu-
other hierarchical structures with different electroactive mate- docapacitive material and the careful design of the hybrid elec-
rials, including H-TiO2/MnO2,[156,157] MnO2/polyaniline,[158] trode architecture. Furthermore, the ability to quantitatively
MoO3/polypyrrole,[159] MoO3/TiO2,[160] V2O5/polypyrrole,[161] differentiate between the capacitive and diffusion-controlled
and V2O5/PANI.[162] Such hierarchical designs could combine processes assists in tailoring the hybrid electrode for different
the advantages of the two components in terms of providing a applications.
large accessible surface area for charge transfer and a shorter There are several important points to consider regarding the
diffusion path for insertion/extraction of active species, thus topic of pseudocapacitive materials and hybrid electrodes:
improving electrochemical performance compared to the indi-
vidual components. (1) The same electrode material, depending on its structure,
morphology, particle size, and guest ion, may display pseu-
docapacitive or battery-like behavior. The identification of the
4.3.2. Going beyond Binary Hybrids types of such electrode materials through the quantitative
differentiation between capacitive and diffusion-controlled
Ternary hybrid structures have been explored in order to take processes is critically important.
advantage of the different merits of the components (conduc- (2) The development of ternary hybrid structures is a promising
tive additives, pseudocapacitive metal oxides, and/or conducting direction for optimal electrode design as the positive proper-
polymers). One typical ternary electrode composed of MnO2, ties of all components can be combined. A good understand-
CNTs, and PEDOT-PSS demonstrated significant improvement ing of surface chemical interactions between the components
in the electrochemical performance.[163] Each component in the is essential to boost synergistic effects to enhance charge
MnO2/CNTs/PEDOT-PSS hybrid structure contributed to the transfer and storage. This knowledge is extremely lacking for
improved electrochemical properties. The MnO2 nanospheres ternary hybrids, although the charge storage mechanism in
provided high specific capacitance, the CNTs offered high sur- binary structures has been well explained.
face area for the deposition of MnO2 and provided good elec- (3) Going beyond hybrid electrodes, hybrid energy storage devic-
trical conductivity and mechanical stability, and the PEDOT-PSS es consisting of a Faradaic battery-type electrode and a Farada-
acted as an effective dispersant for the MnO2/CNTs composite, ic pseudocapacitive or a non-Faradaic double layer electrode,
and a good conductive binder for ensuring good electric con- or consisting of hybrid battery-capacitor electrodes, could be
tact between the MnO2 nanoparticles and CNTs. In addition, promising alternatives to break the energy density limita-
PEDOT-PSS is also an electroactive material that provided extra tion of traditional electrochemical capacitors and the kinetic
pseudocapacitance. Such synergistic effects were also identi- limitation of batteries. The key challenge lies in a thorough
fied in other alternative ternary structures, for example, MnO2/ understanding of the basic electrochemistry of the double
graphene/CNTs, MnO2/graphene/PEDOT-PSS,[164] and MnO2/ hybridization approach. In addition, the selection of appro-
graphene/PANI.[165] The specific capacitance of these electrode priate electrode materials and the design of unique hybrid
electrodes are key factors in realizing the full potential of hy- [22] J. Liu, Graphene-Based Composites for Electrochemical Energy
brid electrode materials and hybrid energy storage devices. Storage, Springer, Singapore 2017.
[23] P. Simon, Y. Gogotsi, B. Dunn, Science 2014, 343, 1210.
[24] B. E. Conway, J. Electrochem. Soc. 1991, 138, 1539.
[25] Y. Wang, Y. Song, Y. Xia, Chem. Soc. Rev. 2016, 45, 5925.
[26] B. E. Conway, W. G. Pell, J. Solid State Electrochem. 2003, 7, 637.
Acknowledgements [27] M. D. Stoller, R. S. Ruoff, Energy Environ. Sci. 2010, 3, 1294.
[28] A. K. Shukla, S. Sampath, K. Vijayamohanan, Curr. Sci. 2000, 79,
This work was supported by the Ministry of Education, Singapore, Tier 1656.
2 (MOE2015-T2-1-148) and Tier 1 (Grant No. M4011424.110), and the
[29] E. Raymundo-Piñero, K. Kierzek, J. Machnikowski, F. Béguin,
National Natural Science Foundation of China (21522602, 91534202).
Carbon 2006, 44, 2498.
[30] A. B. Fuertes, M. Sevilla, ChemSusChem 2015, 8, 1049.
[31] E. Senokos, V. Reguero, J. Palma, J. J. Vilatela, R. Marcilla,
Conflict of Interest Nanoscale 2016, 8, 3620.
[32] X. Yang, C. Cheng, Y. Wang, L. Qiu, D. Li, Science 2013, 341, 534.
The authors declare no conflict of interest. [33] J. R. Miller, R. A. Outlaw, B. C. Holloway, Electrochim. Acta 2011,
56, 10443.
[34] Y. J. Oh, J. J. Yoo, Y. I. Kim, J. K. Yoon, H. N. Yoon, J.-H. Kim,
S. B. Park, Electrochim. Acta 2014, 116, 118.
Keywords [35] Y. W. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. W. Cai,
advanced energy storage devices, analytical methods, P. J. Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz, M. Thommes,
pseudocapacitance, rational materials design D. Su, E. A. Stach, R. S. Ruoff, Science 2011, 332, 1537.
[36] C. T. Hsieh, H. Teng, Carbon 2002, 40, 667.
Received: June 29, 2017 [37] C. Largeot, C. Portet, J. Chmiola, P.-L. Taberna, Y. Gogotsi,
Revised: August 16, 2017 P. Simon, J. Am. Chem. Soc. 2008, 130, 2730.
Published online: November 15, 2017 [38] J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon,
P. L. Taberna, Science 2006, 313, 1760.
[39] H. Ji, X. Zhao, Z. Qiao, J. Jung, Y. Zhu, Y. Lu, L. L. Zhang,
A. H. MacDonald, R. S. Ruoff, Nat. Commun. 2014, 5.
[1] B. Dunn, H. Kamath, J.-M. Tarascon, Science 2011, 334, 928. [40] C. Li, D. Wang, T. Liang, G. Li, X. Wang, M. Cao, J. Liang, Sci.
[2] Z. Yang, J. Zhang, M. C. W. Kintner-Meyer, X. Lu, D. Choi, China, Ser. E: Technol. Sci.46, 349.
J. P. Lemmon, J. Liu, Chem. Rev. 2011, 111, 3577. [41] N. Morimoto, T. Kubo, Y. Nishina, Sci. Rep. 2016, 6, 21715.
[3] H. Kim, J. Hong, K.-Y. Park, H. Kim, S.-W. Kim, K. Kang, Chem. [42] D. Gueon, J. H. Moon, ACS Appl. Mater. Interfaces 2015, 7,
Rev. 2014, 114, 11788. 20083.
[4] M. Winter, R. J. Brodd, Chem. Rev. 2004, 104, 4245. [43] J. W. Jeon, R. Sharma, P. Meduri, B. W. Arey, H. T. Schaef,
[5] J. Desilvestro, O. Haas, J. Electrochem. Soc. 1990, 137, C5. J. L. Lutkenhaus, J. P. Lemmon, P. K. Thallapally, M. I. Nandasiri,
[6] G. L. Soloveichik, Annu. Rev. Chem. Biomol. Eng. 2011, 2, 503. B. P. McGrail, S. K. Nune, ACS Appl. Mater. Interfaces 2014, 6,
[7] E. S. Asscociation, http://energystorage.org/ (accessed: January 7214.
2016). [44] H. C. Youn, S. M. Bak, M. S. Kim, C. Jaye, D. A. Fischer, C. W. Lee,
[8] I. Z. J. I. San Martin, J. J. San Martin, V. Aperribay, P. Eguia, X. Q. Yang, K. C. Roh, K. B. Kim, ChemSusChem 2015, 8, 1875.
European Association for the Development of Renewable Energies, [45] S. Zhang, A. Ikoma, K. Ueno, Z. Chen, K. Dokko, M. Watanabe,
Environment and Power Quality, Energy Storage Technologies for ChemSusChem 2015, 8, 1608.
Electric Applications, Spain 2011. [46] J. Zhou, J. Lian, L. Hou, J. Zhang, H. Gou, M. Xia, Y. Zhao,
[9] B. E. Conway, Electrochemical Supercapacitors: Scientific Fundamen- T. A. Strobel, L. Tao, F. Gao, Nat. Commun. 2015, 6.
tals and Technological Applications, Springer Science + Business [47] K. Fic, E. Frackowiak, F. Beguin, J. Mater. Chem. 2012, 22, 24213.
Media, New York 1999. [48] R. Lin, P. L. Taberna, S. Fantini, V. Presser, C. R. Pérez, F. Malbosc,
[10] L. L. Zhang, X. S. Zhao, Chem. Soc. Rev. 2009, 38, 2520. N. L. Rupesinghe, K. B. K. Teo, Y. Gogotsi, P. Simon, J. Phys. Chem.
[11] Pike Research, Vol. 2015, 2010. Lett. 2011, 2, 2396.
[12] C. Merlet, B. Rotenberg, P. A. Madden, P.-L. Taberna, P. Simon, [49] G. Z. Chen, Prog. Nat. Sci.: Mater. Int. 2013, 23, 245.
Y. Gogotsi, M. Salanne, Nat. Mater. 2012, 11, 306. [50] W. Chen, R. B. Rakhi, H. N. Alshareef, J. Mater. Chem. A 2013, 1,
[13] C. Portet, G. Yushin, Y. Gogotsi, J. Electrochem. Soc. 2008, 155, 3315.
A531. [51] H. Wang, L. Liu, R. Wang, D. Zhang, L. Zhu, S. Qiu, Y. Wei, X. Jin,
[14] S. P. Jahromi, A. Pandikumar, B. T. Goh, Y. S. Lim, W. J. Basirun, Z. Zhang, J. Mater. Chem. A 2015, 3, 8062.
H. N. Lim, N. M. Huang, RSC Adv. 2015, 5, 14010. [52] B. E. Conway, Prog. Surf. Sci. 1984, 16, 1.
[15] H. Jiang, T. Zhao, J. Ma, C. Yan, C. Li, Chem. Commun. 2011, 47, [53] B. E. Conway, Prog. Surf. Sci. 1995, 49, 331.
1264. [54] T. Brousse, D. Bélanger, J. W. Long, J. Electrochem. Soc. 2015, 162,
[16] H. Jiang, L. Yang, C. Li, C. Yan, P. S. Lee, J. Ma, Energy Environ. Sci. A5185.
2011, 4, 1813. [55] K. Engelsmann, W. J. Lorenz, E. Schmidt, J. Electroanal. Chem.
[17] H. Jiang, J. Ma, C. Li, J. Mater. Chem. 2012, 22, 16939. 1980, 114, 1.
[18] V. Augustyn, P. Simon, B. Dunn, Energy Environ. Sci. 2014, 7, 1597. [56] F. G. Will, C. A. Knorr, Z. Elektrochem. 1960, 64, 258.
[19] P. J. Hall, M. Mirzaeian, S. I. Fletcher, F. B. Sillars, A. J. R. Rennie, [57] B. E. Conway, Electrochim. Acta 1993, 38, 1249.
G. O. Shitta-Bey, G. Wilson, A. Cruden, R. Carter, Energy Environ. [58] S. Hadzijordanov, H. Angersteinkozlowska, B. E. Conway, J. Elec-
Sci. 2010, 3, 1238. troanal. Chem. 1975, 60, 359.
[20] R. Kotz, M. Carlen, Electrochim. Acta 2000, 45, 2483. [59] V. Subramanian, S. C. Hall, P. H. Smith, B. Rambabu, Solid State
[21] H. I. Becker, Google Patents, 1957. Ionics 2004, 175, 511.
[60] H. Xia, Y. S. Meng, G. Yuan, C. Cui, L. Lu, Electrochem. Solid State [98] L. Bing, Y. Huatang, Z. Yunshi, Z. Zuoxiang, S. Deying, J. Power
Lett. 2012, 15, A60. Sources 1999, 79, 277.
[61] H. Jiang, C. Li, T. Sun, J. Ma, Nanoscale 2012, 4, 807. [99] D. A. Corrigan, R. M. Bendert, J. Electrochem. Soc. 1989, 136, 723.
[62] H. Jiang, T. Sun, C. Li, J. Ma, J. Mater. Chem. 2012, 22, 2751. [100] V. Augustyn, J. Come, M. A. Lowe, J. W. Kim, P.-L. Taberna,
[63] J. L. Liu, J. Sun, L. A. Gao, J. Phys. Chem. C 2010, 114, 19614. S. H. Tolbert, H. D. Abruna, P. Simon, B. Dunn, Nat. Mater. 2013,
[64] H. Wang, J. Liu, Z. Chen, S. Chen, T. C. Sum, J. Lin, Z. X. Shen, 12, 518.
Electrochim. Acta 2017, 230, 236. [101] J. Come, P. L. Taberna, S. Hamelet, C. Masquelier, P. Simon,
[65] C. Xu, J. Sun, L. Gao, J. Mater. Chem. 2011, 21, 11253. J. Electrochem. Soc. 2011, 158, A1090.
[66] H. P. de Oliveira, S. A. Sydlik, T. M. Swager, J. Phys. Chem. C 2013, [102] D. M. MacArthur, J. Electrochem. Soc. 1970, 117, 729.
117, 10270. [103] J. Wang, J. Polleux, J. Lim, B. Dunn, J. Phys. Chem. C 2007, 111,
[67] H. Zhang, J. Li, C. Gu, M. Yao, B. Yang, P. Lu, Y. Ma, J. Power 14925.
Sources 2016, 332, 413. [104] M. Sathiya, A. S. Prakash, K. Ramesha, J. M. Tarascon,
[68] L. Ran, C. S. Il, L. S. Bok, Nanotechnology 2008, 19, 215710. A. K. Shukla, J. Am. Chem. Soc. 2011, 133, 16291.
[69] J. P. Zheng, T. R. Jow, J. Electrochem. Soc. 1995, 142, L6. [105] H. Lindstrom, S. Sodergren, A. Solbrand, H. Rensmo, J. Hjelm,
[70] M. Toupin, T. Brousse, D. Belanger, Chem. Mater. 2004, 16, 3184. A. Hagfeldt, S. E. Lindquist, J. Phys. Chem. B 1997, 101, 7717.
[71] K. Doblhofer, C. Zhong, Synth. Met. 1991, 43, 2865. [106] M. Zukalova, M. Kalbac, L. Kavan, I. Exnar, M. Graetzel, Chem.
[72] J. Tanguy, M. Hoclet, Synth. Met. 1991, 43, 2995. Mater. 2005, 17, 1248.
[73] F. Béguin, V. Presser, A. Balducci, E. Frackowiak, Adv. Mater. 2014, [107] B. Laskova, M. Zukalova, A. Zukal, M. Bousa, L. Kavan, J. Power
26, 2219. Sources 2014, 246, 103.
[74] P. Liu, X. Wang, Y. Wang, ACS Sustainable Chem. Eng. 2014, 2, [108] C. Chen, Y. Wen, X. Hu, X. Ji, M. Yan, L. Mai, P. Hu, B. Shan,
1795. Y. Huang, Nat. Commun. 2015, 6, 6929.
[75] Q. Yang, S. K. Pang, K. C. Yung, J. Electroanal. Chem. 2014, 728, [109] P. Yu, C. Li, X. Guo, J. Phys. Chem. C 2014, 118, 10616.
140. [110] T. C. Liu, W. G. Pell, B. E. Conway, S. L. Roberson, J. Electrochem.
[76] K. Zhang, L. L. Zhang, X. S. Zhao, J. Wu, Chem. Mater. 2010, 22, Soc. 1998, 145, 1882.
1392. [111] W. Yan, J. Y. Kim, W. Xing, K. C. Donavan, T. Ayvazian,
[77] G. Sun, J. Liu, X. Zhang, X. Wang, H. Li, Y. Yu, W. Huang, R. M. Penner, Chem. Mater. 2012, 24, 2382.
H. Zhang, P. Chen, Angew. Chem., Int. Ed. 2014, 53, 12576. [112] C. Liu, E. I. Gillette, X. Chen, A. J. Pearse, A. C. Kozen,
[78] M. Yang, J. M. Jeong, Y. S. Huh, B. G. Choi, Compos. Sci. Technol. M. A. Schroeder, K. E. Gregorczyk, S. B. Lee, G. W. Rubloff, Nat.
2015, 121, 123. Nanotechnol. 2014, 9, 1031.
[79] H. D. Yoo, Y. Li, Y. Liang, Y. Lan, F. Wang, Y. Yao, ChemNanoMat [113] S. Ardizzone, G. Fregonara, S. Trasatti, Electrochim. Acta 1990, 35,
2016, 2, 688. 263.
[80] H. M. Zeng, Y. Zhao, Y. J. Hao, Q. Y. Lai, J. H. Huang, X. Y. Ji, [114] T. Brezesinski, J. Wang, S. H. Tolbert, B. Dunn, Nat. Mater. 2010,
J. Alloys Compd. 2009, 477, 800. 9, 146.
[81] M. R. Lukatskaya, O. Mashtalir, C. E. Ren, Y. Dall’Agnese, P. Rozier, [115] T. Brezesinski, J. Wang, J. Polleux, B. Dunn, S. H. Tolbert, J. Am.
P. L. Taberna, M. Naguib, P. Simon, M. W. Barsoum, Y. Gogotsi, Chem. Soc. 2009, 131, 1802.
Science 2013, 341, 1502. [116] J. Duay, S. A. Sherrill, Z. Gui, E. Gillette, S. B. Lee, ACS Nano 2013,
[82] M. Ghidiu, M. R. Lukatskaya, M.-Q. Zhao, Y. Gogotsi, 7, 1200.
M. W. Barsoum, Nature 2014, 516, 78. [117] T. Brousse, M. Toupin, R. Dugas, L. Athouel, O. Crosnier,
[83] H. Angersteinkozlowska, J. Klinger, B. E. Conway, J. Electroanal. D. Belanger, J. Electrochem. Soc. 2006, 153, A2171.
Chem. 1977, 75, 61. [118] S. Devaraj, N. Munichandraiah, J. Phys. Chem. C 2008, 112, 4406.
[84] H. Angersteinkozlowska, J. Klinger, B. E. Conway, J. Electroanal. [119] J. M. Miller, B. Dunn, T. D. Tran, R. W. Pekala, J. Electrochem. Soc.
Chem. 1977, 75, 45. 1997, 144, L309.
[85] H. Angersteinkozlowska, B. E. Conway, J. Electroanal. Chem. 1979, [120] T. R. Jow, J. P. Zheng, J. Electrochem. Soc. 1998, 145, 49.
95, 1. [121] Y. Huang, H. Li, Z. Wang, M. Zhu, Z. Pei, Q. Xue, Y. Huang,
[86] Y. G. Wang, H. Q. Li, Y. Y. Xia, Adv. Mater. 2006, 18, 2619. C. Zhi, Nano Energy 2016, 22, 422.
[87] Z. Feng, D. Mo, W. Zhou, Q. Zhou, J. Xu, B. Lu, S. Zhen, Z. Wang, [122] Y. Huang, M. Zhu, Z. Pei, Y. Huang, H. Geng, C. Zhi, ACS Appl.
X. Ma, New J. Chem. 2016, 40, 2304. Mater. Interfaces 2016, 8, 2435.
[88] Q. Mahmood, W. S. Kim, H. S. Park, Nanoscale 2012, 4, 7855. [123] T. Liu, L. Finn, M. Yu, H. Wang, T. Zhai, X. Lu, Y. Tong, Y. Li, Nano
[89] L. Li, S. Peng, H. B. Wu, L. Yu, S. Madhavi, X. W. Lou, Adv. Energy Lett. 2014, 14, 2522.
Mater. 2015, 5, 1500753. [124] A. M. Bryan, L. M. Santino, Y. Lu, S. Acharya, J. M. D’Arcy, Chem.
[90] L. Kong, C. Zhang, J. Wang, W. Qiao, L. Ling, D. Long, ACS Nano Mater. 2016, 28, 5989.
2015, 9, 11200. [125] Y. Shi, L. Peng, Y. Ding, Y. Zhao, G. Yu, Chem. Soc. Rev. 2015, 44,
[91] D. Galizzio, F. Tantardi, S. Trasatti, J. Appl. Electrochem. 1974, 4, 6684.
57. [126] M. Wei, K. Wei, M. Ichihara, H. Zhou, Electrochem. Commun.
[92] W. Sugimoto, H. Iwata, K. Yokoshima, Y. Murakami, Y. Takasu, 2008, 10, 1164.
J. Phys. Chem. B 2005, 109, 7330. [127] J. R. Li, Z. L. Tang, Z. T. Zhang, Chem. Mater. 2005, 17, 5848.
[93] C. Wan, L. Yuan, H. Shen, Int. J. Electrochem. Sci. 2014, 9, 4024. [128] J. R. Li, Z. L. Tang, Z. T. Zhang, Electrochem. Solid State Lett. 2005,
[94] M. R. Lukatskaya, S.-M. Bak, X. Yu, X. Q. Yang, M. W. Barsoum, 8, A570.
Y. Gogotsi, Adv. Energy Mater. 2015, 5, 1500589. [129] J. R. Li, Z. L. Tang, Z. T. Zhang, Chem. Phys. Lett. 2006, 418, 506.
[95] F. Hu, W. Li, J. Zhang, W. Meng, J. Mater. Sci. Technol. 2014, 30, [130] J. Yang, L. Lian, P. Xiong, M. Wei, Chem. Commun. 2014, 50, 5973.
321. [131] D. V. Bavykin, J. M. Friedrich, F. C. Walsh, Adv. Mater. 2006, 18,
[96] K. Brezesinski, J. Wang, J. Haetge, C. Reitz, S. O. Steinmueller, 2807.
S. H. Tolbert, B. M. Smarsly, B. Dunn, T. Brezesinski, J. Am. Chem. [132] X. Luan, Y. Wang, J. Mater. Sci. Technol. 2014, 30, 839.
Soc. 2010, 132, 6982. [133] H. Zhang, G. R. Li, L. P. An, T. Y. Yan, X. P. Gao, H. Y. Zhu, J. Phys.
[97] P. V. Kamath, M. F. Ahmed, J. Appl. Electrochem. 1993, 23, 225. Chem. C 2007, 111, 6143.
[134] G.-N. Zhu, C.-X. Wang, Y.-Y. Xia, J. Power Sources 2011, 196, 2848. [149] A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon, W. Van Schalkwijk,
[135] L. Mai, B. Hu, W. Chen, Y. Qi, C. Lao, R. Yang, Y. Dai, Z. L. Wang, Nat. Mater. 2005, 4, 366.
Adv. Mater. 2007, 19, 3712. [150] B. Wang, J. B. Bates, F. X. Hart, B. C. Sales, R. A. Zuhr,
[136] I. Shakir, M. Sarfraz, Electrochim. Acta 2014, 147, 380. J. D. Robertson, J. Electrochem. Soc. 1996, 143, 3203.
[137] J. W. Kim, V. Augustyn, B. Dunn, Adv. Energy Mater. 2012, 2, 141. [151] J. Cho, Y. J. Kim, B. Park, Chem. Mater. 2000, 12, 3788.
[138] T.-F. Yi, S.-Y. Yang, Y. Xie, J. Mater. Chem. A 2015, 3, 5750. [152] M. Okubo, E. Hosono, J. Kim, M. Enomoto, N. Kojima, T. Kudo,
[139] X. Lu, L. Zhao, X. He, R. Xiao, L. Gu, Y.-S. Hu, H. Li, Z. Wang, H. Zhou, I. Honma, J. Am. Chem. Soc. 2007, 129, 7444.
X. Duan, L. Chen, J. Maier, Y. Ikuhara, Adv. Mater. 2012, 24, 3233. [153] K. Zhu, Q. Wang, J.-H. Kim, A. A. Pesaran, A. J. Frank, J. Phys.
[140] L. Zhao, H.-L. Pan, Y.-S. Hu, H. Li, L.-Q. Chen, Chin. Phys. B 2012, Chem. C 2012, 116, 11895.
21, 028201. [154] T. Brezesinski, J. Wang, R. Senter, K. Brezesinski, B. Dunn,
[141] Y. Sun, L. Zhao, H. Pan, X. Lu, L. Gu, Y.-S. Hu, H. Li, M. Armand, S. H. Tolbert, ACS Nano 2010, 4, 967.
Y. Ikuhara, L. Chen, X. Huang, Nat. Commun. 2013, 4, 1870. [155] Z. Chen, V. Augustyn, X. Jia, Q. Xiao, B. Dunn, Y. Lu, ACS Nano
[142] X. Yu, H. Pan, W. Wan, C. Ma, J. Bai, Q. Meng, S. N. Ehrlich, 2012, 6, 4319.
Y.-S. Hu, X.-Q. Yang, Nano Lett. 2013, 13, 4721. [156] X. Lu, M. Yu, G. Wang, T. Zhai, S. Xie, Y. Ling, Y. Tong, Y. Li, Adv.
[143] M. Naguib, V. N. Mochalin, M. W. Barsoum, Y. Gogotsi, Adv. Mater. 2013, 25, 267.
Mater. 2014, 26, 992. [157] J. Di, X. Fu, H. Zheng, Y. Jia, J. Nanopart. Res. 2015, 17, 1.
[144] M. D. Levi, M. R. Lukatskaya, S. Sigalov, M. Beidaghi, N. Shpigel, [158] K. R. Prasad, N. Miura, Electrochem. Solid State Lett. 2004, 7, A425.
L. Daikhin, D. Aurbach, M. W. Barsoum, Y. Gogotsi, Adv. Energy [159] X. Zhang, X. Zeng, M. Yang, Y. Qi, ACS Appl. Mater. Interfaces
Mater. 2015, 5, 1400815. 2014, 6, 1125.
[145] J. Halim, M. R. Lukatskaya, K. M. Cook, J. Lu, C. R. Smith, [160] D. Guan, X. Gao, J. Li, C. Yuan, Appl. Surf. Sci. 2014, 300, 165.
L.-Å. Näslund, S. J. May, L. Hultman, Y. Gogotsi, P. Eklund, [161] T. Qian, N. Xu, J. Zhou, T. Yang, X. Liu, X. Shen, J. Liang, C. Yan,
M. W. Barsoum, Chem. Mater. 2014, 26, 2374. J. Mater. Chem. A 2015, 3, 488.
[146] M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon, [162] M.-H. Bai, T.-Y. Liu, F. Luan, Y. Li, X.-X. Liu, J. Mater. Chem. A
L. Hultman, Y. Gogotsi, M. W. Barsoum, Adv. Mater. 2011, 23, 2014, 2, 10882.
4248. [163] Y. Hou, Y. Cheng, T. Hobson, J. Liu, Nano Lett. 2010, 10, 2727.
[147] Y. Dall’Agnese, M. R. Lukatskaya, K. M. Cook, P.-L. Taberna, [164] G. Yu, L. Hu, N. Liu, H. Wang, M. Vosgueritchian, Y. Yang, Y. Cui,
Y. Gogotsi, P. Simon, Electrochem. Commun. 2014, 48, 118. Z. Bao, Nano Lett. 2011, 11, 4438.
[148] X. Wang, X. Shen, Y. Gao, Z. Wang, R. Yu, L. Chen, J. Am. Chem. [165] G. Han, Y. Liu, L. Zhang, E. Kan, S. Zhang, J. Tang, W. Tang,
Soc. 2015, 137, 2715. Sci. Rep. 2014, 4, 4824.

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21983844, 2018, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.201700322 by INASP/HINARI - PAKISTAN, Wiley Online Library on [14/01/2023].

Advanced Energy Storage Devices: Basic Principles,

Jilei Liu received his

Hao Jiang received his

dX ideally no or only small potential shifts between the anodic and

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