Supercapacitor Energy Density
Supercapacitor Energy Density
Supercapacitor Energy Density
Graphene fiber based supercapacitors: Strategies and perspective toward high performances
Journal of Energy Chemistry 27, 6 (2018);
Violating the Aufbau principle: an efficient way to improve the stability of luminescent radicals
SCIENCE CHINA Chemistry 62, 1551 (2019);
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Sci China Mater 2018, 61(12): 1517–1526
Green energy storage gadgets and technology have be- allowed supercapacitors to become the next generation of
come significant because of severe energy and environ- energy storage devices. However, they still have low
mental concerns. Presently, commercially available energy densities.
energy storage devices mainly include Li-ion batteries and The energy density of standard supercapacitor devices
supercapacitors [1,2]. Li-ion batteries (LIBs) have been is limited to 10 W h kg−1 [3]. Thus, supercapacitors are
used in many practical applications, such as power sup- presently only used as EV starters and cabin door
plies for portable devices and electric vehicles (EVs), be- switchers for airplanes, which require a high power
cause of their high energy density [3,4]. The highest EV density and a short discharge time. The first advantage of
running distance is over 500 km. However, the drawback using supercapacitors as EV power suppliers is their long
of EVs is the long charging time of up to several hours, cycling life (Table 1), which is superior to the lifetime of
which limits the EV’s mobility. Therefore, selecting an LIBs, which is generally 2,000 times, or 5–6 years if the
appropriate energy storage device is crucial for large- device is charged once daily. However, the lifetime of
format applications, such as EVs (Fig. 1). supercapacitors is much greater than ten years. Further-
Supercapacitors have the advantages of high power more, supercapacitors have a rapid charging time of
density, safety, a broad range of operating temperatures, several minutes or less, which is much less than the time
and superfast charge times [5]. The charging time for a required to fill oil. The bottleneck is the running distance
supercapacitor generally ranges from a few seconds to (energy density), which should be at least 100 km for use
minutes, and the typical cycling life can reach in EVs. Thus, the energy density must also be greater than
100,000 cycles with only a slight performance degrada- 100 W h kg−1. In this case, the mileage goes to infinity
tion. These aforementioned technological features with negligible charging times. EV mobility can be greatly
Research Center of Materials Science, Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications,
Beijing Institute of Technology, Beijing 100081, China
*
Corresponding author (email: cbcao@bit.edu.cn)
enhanced using supercapacitors whose performance is Figure 2 Schematic illustration of various routes to increase energy
competitive with LIBs. density of supercapacitor.
From this perspective, we briefly summarize the state-
of-the-art achievements that have increased the energy
density of supercapacitors and the crucial remaining the resistance [8]. According to this equation, much re-
challenges for developing high-performance super- search has focused on enhancing the energy density of
capacitors. In addition, we highlighted the relevance supercapacitors by improving their capacitance and
between the energy density and key routes, such as the working voltage; the crucial factors for achieving this are
capacitance and working voltage. By summarizing crucial presented in Fig. 2.
factors, such as the surface area, pore size, surface func-
tional groups, high-voltage electrolytes, and various CRUCIAL FACTORS INFLUENCING
supercapacitor device configurations, we aim to provide a CAPACITANCE
summary of recent progress of high-energy-density Considerable research efforts have been devoted to opti-
supercapacitors and identify pathways for developing mizing the structure-influencing factors to achieve high
further advancements in high-energy-density supercapa- capacitance. The capacitance of EDLCs depends on the
citors. surface area and the thickness of the electric double layer
and the dielectric constant. The electrochemical proper-
WORKING PRINCIPLES OF ties mainly relate to the electrode surface area. Some
SUPERCAPACITORS other factors, for example, pore size and structure, surface
Supercapacitors generally comprise two types. The first functional groups, and electrical conductivity, require
type is known as the electric double-layer capacitor additional attention. [9,10].
(EDLC), in which the electrode–electrolyte interface of-
fers capacitance by accumulating electrostatic charges. Specific surface area and pore size
Hence, the capacitance intensively depends on the effec- Increased capacitance is generally associated with higher
tive surface area of the electrode. The other type is the specific surface areas, but this trend is not linear and a
pseudocapacitor, which has electrochemical reactions at higher surface area does not guarantee increased capaci-
the electrode [6]. Thus far, EDLC supercapacitors typi- tance. The specific surface area where the charges can be
cally comprise porous carbon electrodes. These have absorbed is termed the effective surface area, which is
energy densities that are less than 10 W h kg−1, because of related to the pore diameter. Pores can be defined ac-
the low specific capacitance (less than 200 F g−1), and low cording to their diameter as micropores (2 nm), meso-
operating-potential windows that are less than 1.0 V. The pores (2–50 nm), and macropores (50 nm). Generally,
device can be considered as two capacitors attached in higher abundances of micropores and mesopores result in
series because every electrode–electrolyte interface stands higher specific surface areas. However, the specific sur-
for a capacitor [7]. The capacitance is the sum of two face area associated with pores with diameters of less than
electrodes. The capacitance (Cdl) of every interface is 0.4 nm may not contribute to the capacitance [8]. Re-
given by Cdl = εA/4πt, where ε is the dielectric constant, A cently, Simon and Gogotsi et al. [11] demonstrated the
is the effective surface area, and t is the thickness of the relationship between the true pore size and the ion for
electrical double layer. The energy density (E) and power obtaining the maximum capacitance. Furthermore, they
density (P) are calculated as follows: E=1/2CV2, P=V2/4R, reported an exceptional property enhancement for elec-
where C is the DC capacitance, V is the voltage, and R is trode materials with pore sizes of less than 1 nm and
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found the maximum capacitance when the material’s tures, such as nanofiber [21], metal-organic frameworks
pore size was approximately similar to the size of the (MOFs)/graphene aerogel [22], and graphene
electrolyte ions [5]. A strong debate remains regarding foam/reduced graphene oxide [23], can be treated with
the optimal pore size and surface area for enhancing pyrrole, NH4OH, and/or NH3 to obtain N-doped elec-
electrode properties. Recently, Ruoff and coworkers re- trodes. In the in situ preparation method, different
ported activated graphene with a surface area of up to N-containing precursors are used to synthesize N-doped
2,400 m2 g−1 and pore widths of 0.6–5 nm, which have an carbon materials, including polypyrrole [24], poly-
energy density of up to 20 W h kg−1 depending on the acrylonitrile [25], and nitrogen-containing ionic liquids
device’s weight (70 W h kg−1 based on the active material (ILs) [26]. Moreover, many functional carbon materials
weight) [12]. In addition, recent breakthroughs have are directly derived from natural resources that are of low
achieved improved capacitance through optimizing the cost, have numerous sources, and are environmentally
surface area and pore structure of carbon electrodes, in- friendly [27–35]. Typical examples of reported EDLC
cluding highly porous carbon [13,14,15], porous carbon performance are shown in Table 2. Cao et al. [27] pre-
nanosheets [16,17], and holey graphene frameworks viously reported N-doped porous carbon nanosheets
[18,19]. These materials have established future trends in (HPNC-NS) derived from natural silk. HPNC-NS has a
the use of carbon electrodes. The effects of the surface high degree of N-doping (4.7%) and a large specific
area and pore size have clearly driven the research efforts surface area (2,494 m2 g−1). A high capacitance of
toward understanding the electrolyte ion in pores. 242 F g−1 and a large energy density of 102 W h kg−1
However, it remains a tremendous challenge to fully (48 W h L−1) were obtained on the basis of active material
understand the interaction between the pores and elec- weight in EMIMBF4 IL electrolytes. However, excess ni-
trolyte ions. Considering recent progress, in situ mea- trogen (approximately greater than 15%) reduces the
surement experiments coupled with modeling and electrical conductivity and, in turn, decreases the capa-
simulations will help determine the relevant mechanisms citance and cycling performance. Although tremendous
for predicting the optimal surface area and pore size for research efforts have been devoted to designing various
maximal capacitance. Moreover, controlling the pore size surface functional groups for electrodes, it remains a huge
distribution and structure remain challenging. In situ limitation that capacitance values cannot be absolutely
experiments and modeling/simulations suggest that fab- evaluated from the functional groups present. To max-
ricating electrode materials with narrow pore size dis- imize the capacitance, future work should focus on de-
tributions and proper pore structures would increase the veloping an exhaustive correlation and boosting
energy density of supercapacitors without decreasing the mechanism to understand the relationship between ca-
high power density and long cycling life. pacitance and the functional group.
these developments, EDLCs’ capacitance can be further The voltage for aqueous electrolyte systems is generally
increased both from a material perspective, by designing less than 1.0 V, which explains why a normal super-
high-surface-area and high-electric-conductivity materi- capacitor device has a rather low energy density.
als, and from an engineering perspective, by adding Organic electrolytes have a relatively higher operating
conductive binders and improving device architectures. voltage greater than 2.0 V. The highest voltage devices
Various approaches for material design, such as opti- were generally realized in IL electrolyte systems, in which
mized surface area and pore size, intentionally introduce the voltage can reach more than 3 V, which is comparable
pseudocapacitive heteroatoms into the MOF structure, with those of normal Li-ion batteries. Based on their wide
which can be further developed in the future. voltage windows (>3 V) and high chemical and physical
performances, ILs are attractive candidates for next-gen-
CRUCIAL FACTORS INFLUENCING eration electrolytes.
WORKING VOLTAGE Using ILs to increase the working voltage is a promis-
Except regarding capacitance, the working voltage is very ing way to achieve high energy densities because of their
important for the energy density because its square is broad electrochemical stability window that ranges from
directly proportional to the energy density (E = 1/2CV2). 2.0 to 6.0 V, especially about 4.5 V. Moreover, ILs without
For the same capacitance, a threefold increase in the solvation shells can provide well-identified ion sizes due
working voltage leads to approximately an order of to the absence of a solvent, which enables the with pore
magnitude increase in energy. sizes of electrodes to be optimized. Very recently, Cao
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et al. [31,33] prepared porous carbon with an optimized 4.5 V to provide a wider voltage window, which had an
pore size by taking advantage of the “puffing effect,” energy density that was 61% higher than that of single
which is consistent with previous research whereby ASCs. However, repetitive electrochemical reactions
0.7 nm size pores yield the highest capacitance [11]. In affect the structure of pseudocapacitor materials, which
the EMIMBF4 ion liquid electrolyte, the upper limits are significantly affects their stabilities. Moreover, devices
0.48 and 0.76 nm of BF4− and EMIM+, respectively. Stock fabricated from these material types are difficult to pre-
porous carbon flakes showed a high capacitance pare compared to EDLC devices.
(246 F g−1), and coupled with a high-voltage EMIMBF4 IL
electrolyte (e.g., 3.5 V), the energy density was Negative electrode materials
103 W h kg−1 based on the active material weight. How- Carbon-based materials are the best prospective candi-
ever, ILs typically have a high viscosity and a low ionic dates for negative electrode materials in ASCs owing to
conductivity, which decreases the capacitance. To address their low cost, abundance, nontoxicity, and high elec-
this, mixtures of ILs and organic electrolytes have become tronic conductivity. Among the various carbonaceous
popular. Recently, Duan et al. [18] reported high-energy- materials, AC, carbon nanotubes (CNTs), and graphene
density supercapacitors based on an EMIMBF4/AN mix- have attracted remarkable attention. Kim et al. [55] fab-
ture electrolyte, with an energy density of up to ricated an ASC with functionalized AC as a negative
35 W h kg−1 based on device weight, which can achieve an electrode and MnO2/SiC nanoneedle composites as a
operating voltage of up to 3.5 V. It is expected that positive electrode. The optimized ASC could operate in a
improvements in the working voltage can enable a high voltage window of 0–1.9 V and exhibited a maximum
energy density. In the future, the most urgent task is to energy density of 30.06 W h kg−1. Recently, Qiu et al. [56]
design more appropriate electrolytes that have higher fabricated a 3D electrode structure with vertically aligned
working voltages, high ionic conductivities, optimal ionic CNTs that were directly grown on carbon nanofibers
radii, and a suitable viscosity over a broad temperature (VACNTs/CNFs), which enabled a high specific energy of
range and an appropriate porous structure to adapt to IL 70.7 W h kg−1 (based on the active material weight) and
sizes. 97% retention, even after 20,000 charging/discharging
Despite several influencing factors on the energy den- cycles. Graphene has shown a great combination of
sity, the discussion is divided into several sections for desirable performance properties (conductivity, surface
clarity, and these factors synergistically improve the area, and mechanical strength), which result in better
energy density. The maximal energy density could not be electrochemical properties compared to AC and CNTs.
obtained by only addressing a single issue, unless the Liu et al. [57] proposed a unique curved morphology that
aforementioned influencing factors and issues are further prevents the restacking of graphene nanosheets and
investigated and addressed simultaneously. enables the formation of mesopores that are accessible to
ionic electrolytes, which increases the energy density level
ASYMMETRIC SUPERCAPACITORS (ASCs) to 90 W h kg−1.
Asymmetric supercapacitors (ASCs) are assembled using
two dissimilar electrode materials that offer the distinct Positive electrode materials
advantage of a wide operational voltage window, which Metal oxides have great potential as positive electrode
significantly enhances their energy density. Generally, materials. RuO2, MnO2, and Ni(OH)2 are promising
metal oxides are employed as one of the supercapacitor candidates for positive electrode materials in ASCs owing
electrodes, whereby RuO2, MnO2, and Ni(OH)2 are the to their high specific capacitance and large potential
most commonly used materials [38–49]. Other materials window. Recently, Kaner et al. [58] reported inter-
can be used as the other electrode to fabricate ASCs, such digitated supercapacitors made of 3D porous RuO2
as porous carbon [50]. For example, ASCs employing nanoparticles anchored to graphene sheets. These elec-
aqueous electrolytes have potential windows of greater trodes exhibited an ultrahigh capacitance of 1,139 F g−1
than 2.0 V. The energy density of ASCs can reach almost with an excellent rate capability. Moreover, ASCs
100 W h kg−1 [51–53]. Based on these aforementioned employing graphene sheets/RuO2 as the positive electrode
features, a higher ASC energy density can be obtained by and an AC negative electrode demonstrated an extremely
utilizing organic or ionic-liquid electrolytes, which have high energy density of 55 W h kg−1 at a power density of
higher working voltages. In contrast, Misra et al. [54] 12 kW kg−1. The low surface area and poor electronic
reported a tandem ASC with a high working potential of conductivity of MnO2 are two major problems that hin-
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using K-ion intercalation battery-type electrodes. This is next-generation BSHs are discussed in the following
because the ionic radius of K+ is much larger than those based on the progress attained thus far. (1) Battery-type
of Li+/Na+ and the host materials are scarcely available. electrodes generally have slow redox reactions, which
restricts their power properties. Currently, the most
Acidic BSH common approaches for addressing this problem are to
Lead-acid batteries were developed over one and a half design various nanostructures to shorten the ion trans-
centuries ago, but they still remain one of the most port route and to utilize nanoscale coating with con-
important commercial rechargeable batteries. The ductive species to enhance the conductivity and
hybridization of lead-acid batteries with SC leads to acidic steadiness. In addition to these above approaches, future
BSHs. Among the various BSHs, lead-carbon capacitors research efforts could be directed to designing nanoscale
are superior because of their high voltage (~2.0 V). Fur- doping methods for achieving high power properties. (2)
thermore, recycling PbO2 and sulfuric acid is now an Exploring novel electrode and electrolyte materials
optimized and a financially self-sufficient process. The remains highly desirable, particularly for green Na-ion
lead-carbon capacitor suffers from a low specific energy BSHs. It is an enormous challenge to fabricate high-
density (15–30 W h kg−1) and a low power density due to energy-density Na-ion BSH devices with a high power
the electrochemically active surface of PbO2, which is low density. To overcome this, experimental and various
and hinders rapid redox reactions. computational approaches, such as theory, modeling, and
simulations, are required. The aforementioned compu-
Alkaline BSH tational approaches could direct the design options for
Nickel-cadmium (Ni-Cd) batteries have been used for electrode and electrolyte materials.
~100 years and are the most mature system of alkaline
batteries. Alkaline BSHs refer to the hybrid systems that FUTURE OUTLOOK
employ alkaline aqueous solutions as electrolytes and Here, we have discussed recent progress in designing
carbon materials as the capacitive electrode. The other high-performance supercapacitors, such as symmetric
electrode is based on transition metal oxides/hydroxides and asymmetric supercapacitors, and BSHs. These dis-
that exhibit battery-like performance. Lou et al. synthe- cussions highlighted several ways to increase the capaci-
sized NiMoO4 nanosheet/nanowire array electrodes on tance/working voltage of supercapacitors to address the
different substrates. The resulting NiMoO4/AC alkaline present shortage of low energy densities. Future trends
BSH delivered reasonably high energy and power den- are listed in the following. Firstly, fully exploring novel
sities (60.9 W h kg−1 at 850 W kg−1 and 41.1 W h kg−1 at types of electrodes and electrolyte materials is still
17,002 W kg−1) [68]. Iron oxides are one of the few anode essential regardless of the supercapacitor type. To achieve
candidates for rechargeable alkaline batteries, such as this, diverse experimental and computational investiga-
Ni-Fe batteries, because of their low cost, environmental tions are required, such as theory, modeling, and simu-
friendliness, and natural abundance. However, the ap- lations. Such computational research can direct the
plication of iron oxides in alkaline BSHs has rarely been design options for electrode and electrolyte materials.
investigated. The shortcomings of Fe-oxide anodes are Achieving high-energy-density symmetric super-
their relatively low conductivity and pulverization with capacitors (EDLCs) presently remains a major challenge
cycling or at high current densities (large volume [70–72]. Future work should focus on the increasing
expansion). Li et al. presented a “carbon shell protection” capacitance and working voltage by increasing the spe-
solution and synthesized an Fe3O4-carbon binder-free cific capacitance by enhancing the effective specific sur-
nanorod array anode. With facile carbon coating, the face area, optimizing the pore size and volume, and
volume expansion and the possible structural deforma- providing surface functional groups to increase the
tion were effectively restricted, helping to maintain the pseudocapacitance contribution. Moreover, employing
electrode’s integration; the carbon shell also improved the various ILs, in which voltage can reach more than 3.0 V,
electrical conductivity of the electrode [69]. can significantly increase the energy density. Moreover,
Thus far, BSH properties, especially the energy and the synergetic effect of diverse factors is a promising
power density, cannot compete with advanced batteries breakthrough trend. However, it remains a tremendous
and supercapacitors as most BSH types are still in their challenge to fully understand the interaction between the
primary developmental stage and require vast advance- pores and electrolyte ions. Considering progress, in situ
ments. Some challenges and future developments for measurement experiments coupled with modeling/simu-
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nanosheet and nanorod arrays on various conductive substrates as Acknowledgements This work was financially supported by the Na-
advanced electrodes for asymmetric supercapacitors. Adv Energy tional Natural Science Foundation of China (21371023).
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suitability. Adv Funct Mater, 2015, 25: 5384–5394 Conflict of interest The authors declare no competing interests.
Chuanbao Cao is currently the chief responsible professor of the School of Materials Science and Engineering, Director of
Research Center of Materials Science of Beijing Institute of Technology (BIT), China. His research is focused on the
electrochemical energy storage and conversion including electrode materials of super-capacitors, lithium ion battery, and
photo-electrochemical materials. Until now, he has published more than 300 peer-reviewed research papers, holds or has
filed 50 patents and patent applications.
提高超级电容器能量密度的路线: 进步和展望
吴宇, 曹传宝*
摘要 超级电容器与其他能量存储装置相比具有突出的优势, 例如长循环寿命, 快速的充放电过程以及安全性. 然而, 由于超级电容器仍然
面临着能量密度低的问题, 这限制了其广泛应用. 我们简要综述了影响超级电容器能量密度的因素, 讨论了如何通过提高电容和工作电压
来改善能量密度. 特别地, 我们总结了最近在高能量密度超级电容器方面的一些令人激动的进展, 并着重分析了其未来发展趋势. 最后我
们讨论了多种多样的超级电容器, 并提出了一些关键的设计以获得高能量密度.
1526 . . . . . . . . . . . . . . . . ©. . Science
. . . . China
. . . .Press
. . .and
. . Springer-Verlag
. . . . . . . . .GmbH
. . . .Germany,
. . . . . part
. . .of. Springer
. . . . . Nature
. . . . 2018
. . . . . December 2018 | Vol. 61 No. 12
https://engine.scichina.com/doi/10.1007/s40843-018-9290-y