Featuring work from the research lab of Prof.

Yuping Wu, As featured in:

Nanjing Tech University, China.

Latest advances in supercapacitors: from new electrode

materials to novel device designs

Our research covers lithium batteries, cutting-edge aqueous

batteries, electrolytes, solar hydrogen and supercapacitors.
The technologies of DKJ Co. Ltd., the first company to
commercialize PVDF-based separators, are from this lab.
Here are some examples of novel materials and devices
for electrochemical capacitors.

See Lijun Fu, Qingming Zhou,

Yuping Wu et al.,
Chem. Soc. Rev., 2017, 46, 6816.

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Latest advances in supercapacitors: from new

electrode materials to novel device designs
Cite this: Chem. Soc. Rev., 2017,
46, 6816
Faxing Wang,†abc Xiongwei Wu,†ad Xinhai Yuan,a Zaichun Liu,a Yi Zhang,a Lijun Fu,*a
Yusong Zhu,a Qingming Zhou,*d Yuping Wu *ab and Wei Huanga

Received 28th May 2017
DOI: 10.1039/c7cs00205j
rsc.li/chem-soc-rev
Notably, many significant breakthroughs for a new generation of supercapacitors have been reported in
recent years, related to theoretical understanding, material synthesis and device designs. Herein, we
summarize the state-of-the-art progress toward mechanisms, new materials, and novel device designs
for supercapacitors. Firstly, fundamental understanding of the mechanism is mainly focused on the
relationship between the structural properties of electrode materials and their electrochemical
performances based on some in situ characterization techniques and simulations. Secondly, some
emerging electrode materials are discussed, including metal–organic frameworks (MOFs), covalent
organic frameworks (COFs), MXenes, metal nitrides, black phosphorus, LaMnO3, and RbAg4I5/graphite.
Thirdly, the device innovations for the next generation of supercapacitors are provided successively,
mainly emphasizing flow supercapacitors, alternating current (AC) line-filtering supercapacitors, redox
electrolyte enhanced supercapacitors, metal ion hybrid supercapacitors, micro-supercapacitors (fiber,
plane and three-dimensional) and multifunctional supercapacitors including electrochromic super-
capacitors, self-healing supercapacitors, piezoelectric supercapacitors, shape-memory supercapacitors,
thermal self-protective supercapacitors, thermal self-charging supercapacitors, and photo self-charging
supercapacitors. Finally, the future developments and key technical challenges are highlighted regarding
further research in this thriving field.

1. Introduction density, fast charge/discharge rate and long cycle life.2–5 Super-
capacitors and rechargeable batteries are similar systems with
The development of civilization is directly related to progress in negative electrodes, positive electrodes and separators that
science and technology. Today, someone who could imagine are soaked with electrolytes.1 Normally, supercapacitors are
the reality without electrochemical energy storage systems considered as the intermediate between the battery and the
would see a world without electronic portable devices such as
cellular phones, laptops, or iPods, and also without electric Dr Yuping Wu is a distinguished
vehicles, airplanes, and many other inventions which make professor at Nanjing Tech Univer-
our life easier and more comfortable. In this energy-dependent sity, Nanjing, China. Since 1994,
world, electrochemical devices for energy storage play a vital he has published over 240 peer-
role in overcoming fossil fuel exhaustion.1 Among various reviewed papers, written 6 mono-
electrochemical energy storage devices, supercapacitors have graphs whose sales are above
attracted significant interest in both academia and industry 40 000 copies over the world and
during the past several decades owing to their superior power 10 chapters, translated one book,
and got 24 issued patents. His
a
present H-index is 58. Within 10
School of Energy Science and Engineering, and Institute for Advanced Materials,
Nanjing Tech University, Nanjing 211816, Jiangsu Province, China.
years, 34 papers are listed as ESI
E-mail: wuyp@fudan.edu.cn highly cited papers, and he has
b
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis Yuping Wu been one of the highly cited
and Innovative Materials, Fudan University, Shanghai 200433, China researchers throughout the world
c
Department of Chemistry and Food Chemistry, Technische Universität Dresden,
since 2015. His research has led to the creation of four companies on
01062 Dresden, Germany
d
College of Science, Hunan Agricultural University, Changsha, Hunan 410128,
anode materials, cathode materials, separators and power lithium
China ion batteries, respectively. His research is mainly focused on energy
† These authors contributed equally. storage and conversion systems and solar hydrogen.

6816 | Chem. Soc. Rev., 2017, 46, 6816--6854 This journal is © The Royal Society of Chemistry 2017

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conventional dielectric capacitor. Now, supercapacitors have
been utilized in many applications such as consumer electronics,
transportation, military and aerospace, grid balancing, and power
backup by protecting, enhancing, and/or replacing batteries in
these applications.6–10 For example, they can be used along with
rechargeable batteries to provide the additional power required in
many applications, such as electrical vehicles (EVs) and hybrid
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electric vehicles (HEVs) for capturing and storing energy from
regenerative braking and supplying vehicle acceleration power.
This can protect rechargeable batteries from high-frequency
rapid discharge/charge processes.
Historically, a capacitor was evolved from a Leyden jar
consisting of a glass vessel whose interior and exterior were
coated with metal foils. Those metal foils and the jar acted as
the electrodes and dielectric, respectively. During the charging
process, positive charges gradually accumulate on one plate
while negative charges accumulate on the other plate. When
these two electrodes are connected using a conductive wire with
or without a load, a discharging process occurs.9b Materials that
can be polarized when an electric field is applied are utilized as
dielectric capacitors. The dielectric is generally composed of an
electrical insulation material, such as a vacuum, a non-ionized
gas, a solid such as a ceramic or polymer, or a liquid (aqueous
or non-aqueous electrolyte). In 1886, the use of electrolytes
as dielectrics was initially developed by Charles. Electrolytic
dielectrics include metal oxides (like aluminum oxide and tantalum
pentoxide), aqueous-based liquid electrolytes, and non-aqueous-
based liquid electrolytes. Currently, there are mainly two types
of electrolytic capacitors (aluminum electrolytic capacitors and
tantalum electrolytic capacitors). Since 1930, ceramics have
been widely used to construct capacitors for radio receivers.
These early capacitors were mainly utilized as primary circuit
elements in holding microfarad to picofarad charges of direct
current or to filter the frequencies for alternating current
circuits.9 In 1957, the earliest supercapacitors, electrochemical
double layer capacitors (EDLCs), were invented as an electro-
lytic capacitor for low voltage operation. In 1962, a chemist at
the Standard Oil Company of Ohio refined the carbon–carbon
electrochemical capacitor. For EDLCs, the energy storage
is based on the adsorption of electrolyte ions on the large
specific surface area of electrically conductive porous electrodes.
Typically, carbon materials and their derivatives are used in
EDLCs, including activated carbon, porous carbon, carbon
nanotubes (CNTs), and graphene. To increase the capacitance
and energy density of supercapacitors, some electrochemically
active materials have been explored as electrode materials for
pseudocapacitors. In the case of pseudocapacitance, energy
storage comes from reversible surface faraday redox reactions
occurring at the interface between electrolytes and electroactive
materials. Electrode materials for pseudocapacitors consist
of transition metal oxides (e.g. RuO2, MnO2, and Fe3O4), transi-
tion metal sulfides (e.g. MoS2), carbon materials possessing
oxygen- and nitrogen-containing surface functional groups, and
conducting polymers (e.g. polythiophene (PT), polypyrrole (PPy)
and polyaniline (PANi)).11–18 It should be noted that the electro-
chemical behaviors of some metal oxides/hydroxides/sulfides
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(like Ni(OH)2) have been verified to be a semi-infinite diffusion-
limited reaction process according to the linear relationship of
the current peak (ip) vs. square root of the scan rate (v1/2). These
electrode materials, involving typical diffusion-limited redox
reactions, should be battery-type ones instead of supercapacitor-
type ones. However, it is appropriate to combine these battery-
type electrode materials such as Co3O4, NiO and CoS2 with
capacitive materials for fabricating hybrid supercapacitors.15
If supercapacitors could meet all the requirements of next-
generation electronic devices, everything would be simple and
perfect. Unfortunately, the traditional supercapacitor has a
rigid bulky or planar structure and there is little possibility of
achieving future applications, which require being weaveable,
or miniature, or smart, or large-scale.19–23 To transcend the
limitations, various novel devices of supercapacitors have been
designed to achieve special properties. Thinner, lighter, smart
or even transparent supercapacitors are needed for increasingly
multifunctional consumer electronics. With the emergence of
various types of future electronics, supercapacitors with more
functions and novel features are being sought to extend their
applications. For EDLCs and pseudocapacitors, the most com-
monly used electrode materials for industrial applications are
still activated carbons and metal oxides, respectively. In the
case of activated carbons, they normally exhibit irregular
morphologies, poorly graphitized frameworks, and wide pore
size distributions.24 While the application of metal oxides in
pseudocapacitors is seriously hindered by their relatively low
electronic conductivities, which cannot keep pace with energy
storage in higher rate environments.24c Different from many
inorganic electrode materials, it is easy to control the porous
architectures, pore volumes, and surface areas of MOFs and
COFs, which makes them good candidates for supercapacitors.24,25
Many electrode materials with high electronic conductivity
(such as MXene, metal nitrides, mixed conductors etc.) or with
a special two-dimensional structure (like phosphorene) have
also been investigated during the past several years.26 Another
key component of supercapacitors is the electrolyte. Generally,
there are two types of electrolytes: liquid electrolytes and solid/
quasi-solid-state electrolytes. Currently, solid-state electrolytes
(like Li2S–P2S5 systems) and quasi-solid-state electrolytes (such
as polymer systems) suffer from low ionic conductivities, which
limit the fast charge/discharge ability of supercapacitors.26c
But solid-state electrolytes can avoid the leakage problem of
the liquid electrolytes. Liquid electrolytes can be classified
as aqueous electrolytes, organic electrolytes and ionic liquids
(ILs). Three representative aqueous electrolytes are based on
acid, alkaline, and neutral solutions, possessing high ionic
conductivities but narrow operating voltage windows. Most
commercial supercapacitors use organic electrolytes owing to
their wider operation potential windows, but are sometimes
associated with safety risks because of the flammability, volatility,
and toxicity of the organic electrolytes and improper use such as
overcharge or short-circuit. Ionic liquid electrolytes are hot topics
in supercapacitors owing to their high electrochemical stability,
negligible volatility, and non-flammability. However, their
high viscosity and high cost limit their practical application.1
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Thus, extensive efforts have been devoted to exploring new electro-
lytes to improve the overall performance of supercapacitors. For
example, redox-active electrolyte enhanced devices have emerged
through introducing the pseudocapacitive contribution in the
electrolytes.26d Therefore, on one hand, much effort has been
made toward discovering new electrode materials; while on the
other hand, it is also critically important to produce matching
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devices to power future electronic devices.
Currently, many excellent reviews have overviewed tradi-
tional supercapacitors (like electrode materials and
electrolytes)1–6,8,10–14,16–18 and some novel supercapacitors (like flex-
ible and smart devices).7,19,20 However, there is still no systematic
summary of recent progress in the development of next-generation
supercapacitors, which should cover fundamental understanding,
new emerging materials and device innovations. Accordingly, this
review provides a comprehensive description of the latest scientific
progress toward supercapacitors, which is divided into three main
sections including mechanisms, new electrode materials, and novel
device designs (Fig. 1). In particular, this work will first briefly
present an overview of the development on mechanisms based on
some in situ characterization techniques and ab initio simulation.
This section is intended to examine recent progress in EDLC and
pseudocapacitors, highlighting the fundamental understanding of
the charge storage mechanisms, and transport pathways of electrons
and ions. Then, we present a summary of the recent progress in the
development of new electrode materials, such as MOFs, COFs,
Fig. 1 An overview of the latest advances on materials and devices of supercapacitors (SCs). The latest emerging electrode materials and device designs
will be discussed.
6818 | Chem. Soc. Rev., 2017, 46, 6816--6854
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Mxene, metal nitrides, black phosphorus, LaMnO3, MxMnO2 and
RbAg4I5/graphite. In this section, an emphasis is put on the synthetic
strategies and the related electrochemical properties. The next
section details the state-of-the-art research activities in the area of
device innovations for the next generation of supercapacitors,
including flow supercapacitors, alternating current (AC) line-
filtering supercapacitors, redox electrolyte enhanced supercapaci-
tors, metal ion hybrid supercapacitors, micro-supercapacitors
(fiber, plane and 3D) and multifunctional supercapacitors includ-
ing electrochromic supercapacitors, self-healing supercapacitors,
piezoelectric supercapacitors, shape-memory supercapacitors,
thermal self-protection supercapacitors, thermal self-charging
supercapacitors, and photo self-charging supercapacitors. A parti-
cular focus is directed to their design principles and special
functions. To facilitate further research and development, some
future research trends and directions are finally discussed. This
review is aimed at providing readers with a comprehensive insight
into the fundamental understanding, new electrode materials and
novel device designs of supercapacitors.
2. New findings on mechanisms
2.1 EDLCs
For the past several decades, researchers thought that the best
strategy for increasing the capacitance of EDLCs was to increase
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the specific surface area (SSA) of carbon materials. The high
surface-to-volume ratio arises from the porosity. Normally, the
pore size in porous EDLCs should be approximately twice the
ion size to allow the coverage of the pore walls. One may expect
that the capacitance would decrease by decreasing the pore size
as fewer ions can enter a pore. Solvated ions often were not
believed to enter the pores if the size exceeded the pore
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dimensions. However, this ‘common sense’ reasoning was
experimentally negated by the report of a huge increase in
the specific capacitance with decreasing pore width for pores
smaller than double the size of the bare ions.26,27 Actually, there
is not a clear correlation between specific surface area and the
specific capacitance. Increasing the SSA with a simultaneous
increase in the average pore size does not result in an increase
in the specific capacitance.28 Interestingly, using microporous
carbons with pores smaller than 1 nm enabled the volumetric
capacitance to increase from 55 to 80 F cm3.26 Monte Carlo
simulations suggested that the ‘anomalous’ increase of the
capacitance with decreasing pore width resulted from exponen-
tial screening of the electrostatic interactions of ions inside a
pore, as well as the image-charge attraction of ions to the pore
surface.29 Recently, researchers came to realize that the pore
size and the carbon nanostructure (rather than specific surface
area) played a more crucial role in increasing the specific
capacitance.30,31 With the help of various in situ spectroscopies
and advanced simulation techniques, understanding the physi-
cal processes and underlying the charge storage mechanisms
became hot spots for carbon-based supercapacitors.
The charge storage in supercapacitors was traditionally
attributed to a simple mechanism of the applied potential
driving the ions into the porous carbon network.9 For activated
carbon used for supercapacitors in the electrolyte of tetraethyl-
phosphonium tetrafluoroborate (PEt4–BF4) salt dissolved in
acetonitrile (ACN), the in situ 31P NMR spectra showed an
increase in the in-pore cation population for the negative
voltage range, because cations were absorbed into the micro-
pores. This is consistent with the classical charge separation
occurring upon polarization at the electrode/electrolyte inter-
face. In other words, ions of opposite charge were adsorbed
onto the surface to form an electric double layer. However, the
charging mechanism was not a purely adsorptive process for
the positive polarization. Its charge storage was normally driven
by exchange of the cations for anions, whereby anions were
absorbed into the micropores while cations were simultaneously
ejected. In the negative voltage range, the in-pore cation popula-
tion increases while there were no significant changes in the
in-pore anion populations (Fig. 2a). Thus, charge storage in the
negative voltage range was dominated by counter-ion adsorp-
tion, which meant cation adsorption dominates the negative
polarization.32 Therefore, the charge storage mechanisms were
different for positively and negatively polarized electrodes.
Moreover, the adsorbed ions were only partially solvated. The
slope of a linear fit of the experimental mass change versus
charge presented an experimental molar mass of 369 g mol1
per adsorbed species (Fig. 2b). When the adsorbed species are
PEt4+ cations, the cation solvation number, based on the NMR
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Fig. 2 Some new findings on mechanisms for EDLCs based on in situ
NMR, EQCM and IR. (a) In-pore ion populations for activated carbon based
supercapacitors in 0.5 M PEt4–BF4/ACN at different states of charge in the
range of 1.5 V to +1.5 V. (b) EQCM data for activated carbon based
supercapacitors in a 0.75 M PEt4–BF4/ACN electrolyte. Calculated mass
changes were based on a purely adsorptive mechanism (green triangles)
and an ion exchange mechanism (orange squares) (modified from ref. 32,
copyright permission from Nature Publishing Group). The normalized
absorbance of the infrared bands of the cation and anion as a function
of time during CV cycles from 1.5 to +1.5 V at a scan rate of 5 mV s1
for (c) CDC electrodes and (d) OLC electrodes (modified from ref. 40,
copyright permission from the American Chemical Society).
results, was estimated to be 5.4, which is slightly lower than the
solvation number of 7 predicted for chemically similar NEt4+
cations in bulk solution.32 This suggested that cations were
partially desolvated when they entered the pores of the micro-
porous carbon.
Molecular dynamics (MD) simulations confirmed the
phenomenon of ion confinement in carbon nanopores.33 That
is to say, ions in electrolytes lose a part of their solvation shell
to access these small nanopores. Such desolvation and the local
charge stored on the electrode increase with the degree of
confinement. The degree of confinement has a substantial
influence upon the local charge stored on the electrode surface.
The solvation numbers around ions can be quantified directly
using an electrochemical quartz crystal micro-balance (EQCM).
For carbide-derived carbon (CDC) using EMI-TFSI in aceto-
nitrile as an electrolyte, the solvation numbers around the
cation in 1 and 0.65 nm pores are estimated to be 3–4 and 1–2,
respectively.34 Less solvated solvent molecules in a 0.65 nm
pore than in a 1 nm-pore suggested that the ion desolvation
occurred to fit in the smaller pores.
From MD simulation results, the capacitance versus pore
size was found to exhibit two peaks located at 0.7 and 1.4 nm,
respectively. Specifically, as the pore shrinks from 1.0 to 0.7 nm
or expands from 1 to 1.4 nm, the capacitance of the micropore
increases anomalously in a 1-ethyl-3-methylimidazolium
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(EMIM)-based ionic liquid electrolyte.35–37 Actually, large capa-
citance can be expected if the ion solvation is weak (as in the
0.7 nm pore) or if the electrification of a pore disrupts the
inside strong ion solvation structure (as in the about 1.3 nm
pore).37 Similarly, the classical DFT method showed that the
capacitance displayed multiple peaks with a decaying envelope
as the pore size increases from one to many times the ion
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diameter.38 The maximum capacitance was obtained when the
pore size was comparable to ion diameters (0.7 nm). At this
point, the pore size was perfectly adapted to the ion size and
ion adsorption was achieved in the most efficient way. When
the pore size was decreased below 0.68 nm, there was less and
less space available for double layer charges since ions cannot
get into the smallest pores.27 MD simulations also showed that
charging subnanometer pores with ionic liquids was often
accompanied by overfilling, which could accelerate charging.39
While the de-filling slows down charging significantly, and this
would reduce the power density of EDLCs. One way to relieve it is
to make pores ionophobic by eliminating overfilling/de-filling.
Ionophobic pores can accelerate charging by an order of magni-
tude compared to conventional and ionophilic pores.
Apart from the pore sizes, carbon nanostructures also
show great influence on the physical processes underlying the
charge storage mechanisms. The ion dynamics of 1-ethyl-3-
methylimidazolium bis-((trifluoromethyl)sulfonyl)imide (EMIM-
TFSI) in electrodes made of porous nanosized CDCs and
nonporous onion-like carbons (OLCs) were investigated at a
molecular level using an in situ infrared spectroelectrochemical
technique.40 Electrolyte ions (both cations and anions) could
enter the pores of CDCs, while only occupying the surface
of OLCs without long-range ion transport through the bulk
electrode. In Fig. 2c, it is shown that the absorbances of both
the cation and anion decreased with the voltage increasing
from 0 to +1.5 V, suggesting that ions enter the pores of the
CDC particles. When the voltage reverts from +1.5 V to 0 V, the
absorbance increased and reached a maximum as the voltage
approaches 0 V, indicating that ions are expelled from the
pores. Then with the voltage scanning from 0 V in the negative
direction, the absorbance began to decrease again as ions
re-enter the pores. When the voltage approached 1.5 V, the
absorbance of both the cation and anion reached a new minimum
as the pores again fill with ions. However, only a small change in
absorbance was observed for the CDC electrodes (Fig. 2d), which
was similar to the change in absorbance for a supercapacitor only
with the current collectors (without any carbon). Sometimes, it is
very hard to compare different studies due to large differences in
the materials’ structure, binder content, crystallinity, and, more
importantly, pore size distribution.
2.2 Pseudocapacitors
For many years, the term ‘pseudocapacitance’ was synonymous
with surface redox reactions. However, more recently, the concept
of ‘intercalation pseudocapacitance’ was proposed.41–44 Due to the
pursuit of high-energy supercapacitors while maintaining high
power and long cycling life, continuous reports on the combi-
nation between rechargeable batteries and supercapacitors are
6820 | Chem. Soc. Rev., 2017, 46, 6816--6854
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creating electrode materials with new reaction mechanisms for
ultra-fast charge/discharge and high rate performance. Through
physical control of electrode materials (including particle
size, surface area, electronic conductivity, phase structure, and
crystalline), scientists discovered the existence of pseudocapaci-
tance contribution in some electrode materials for metal ion
batteries, which is named as ‘intercalation pseudocapacitance’.
Currently, the most widely investigated electrode materials for
intercalation pseudocapacitance are mainly nanostructured TiO2
(B), Nb2O5 and MoO3 in organic electrolytes.41–44
The capacitive effect can be characterized by analyzing the
cyclic voltammetric data at various sweep rates according
to eqn (1):
i = avb, (1)
where i is the current (A) and v is the sweep rate (mV s1) of a
cyclic voltammetry experiment, and a and b are adjustable
parameters. The b-values are determined from the slope of
the plot of log(i) vs. log(v). As is well-known, a b-value of 0.5
generally indicates a diffusion controlled faradaic intercalation
process, which is normally a battery behavior. In this case, the
current is proportional to the square root of the sweep rate, v,
according to eqn (2):
i = nFAC*D1/2v1/2(anF/RT)1/2p1/2w(bt), (2)
where C* is the surface concentration of the electrode material;
a is the transfer coefficient; D is the chemical diffusion coeffi-
cient; n is the number of electrons involved in the electrode
reaction; A is the surface area of the electrode material; F is
the Faraday constant; R is the molar gas constant; T is the
temperature; and the function (bt) represents the normalized
current. In contrast, typical capacitive behavior is not diffusion-
controlled and the capacitive current is proportional to the
sweep rate, according to eqn (3):
i = CdAv, (3)
where Cd represents the capacitance and A is the surface area
of the active materials. As reported, to better understand the
capacitance contribution to the total charge storage, the total
current resulting from capacitive effects (k1v) and diffusion
controlled Faradic processes (k2v1/2) can be represented as:
i = k1v + k2v1/2, (4)
or i/v1/2 = k1v1/2 + k2. (5)
After interpreting the results from CV curves with various scan
rates, one can determine the k1 and k2 values, as well as the
capacitive current contribution at a given potential, by plotting
i/v1/2 versus v1/2.45–49 In fact, the intercalation pseudocapacitive
behavior displays kinetics that is similar to typical pseudo-
capacitive behavior. One of the more popular approaches to
develop intercalation pseudocapacitive materials involves the
synthesis of nanoscale materials. Taking mesoporous iso-oriented
a-MoO3 as an example, the capacitive contribution occupied 70%
of the total charge storage (Fig. 3a).43 The capacitive contribution
for the mesoporous a-MoO3 crystalline films was significantly
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Fig. 3 Cyclic voltammetric (CV) behaviors of MoO3. (a) CV curves of meso-
porous MoO3 films at a sweep rate of 0.1 mV s1; (b) the calculated b-value at
different potentials during a cathodic sweep (modified from ref. 43); CV curves
of thin-film (c) MoO3x and (d) MoO3 electrodes. The capacitive contribution
to the total current is shown by the shaded region (modified from ref. 50)
(Copyright permission from Nature Publishing Group).
higher than that for the amorphous ones. The charge storage
mechanism involved in mesoporous a-MoO3 is not controlled
by semi-infinite diffusion but more close to a surface-controlled
diffusion with the b-value varying from 0.8 to 1.0 in the
potential range of 1.5–2.6 V (vs. Li+/Li) (Fig. 3b). At 2.4 V and
2.1 V (vs. Li+/Li), respectively, the b-values are smaller, which
indicates that the current arises from capacitive effects mixed
with contributions from the diffusion-controlled Li+ ion inter-
calation reaction. But the major part of the total stored charge
is capacitive. Very recently, the introduction of oxygen vacancies
into a-MoO3 led to a larger interlayer spacing that promotes faster
charge storage kinetics with intercalation pseudocapacitive
behavior.50 The intercalation pseudocapacitive charge storage
for MoO3x was two times larger than that for MoO3 (Fig. 3c
and d). No phase transition occurred in MoO3x because the
expanded lattice galleries were apparently large enough that a
phase transition was no longer energetically needed to accom-
modate Li+ ions in the structure.
There are two important considerations for intercalation
pseudocapacitive materials: (1) the structure is not accompa-
nied by a phase transformation upon intercalation and (2) the
b-value in eqn (1) should be equal/or close to 1. Mesoporous
and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5) offer
two-dimensional transport pathways and little structural change
on Li+ ion intercalation. Thus even a 40 mm thick T-Nb2O5
electrode still exhibited very fast charge/discharge characteristics
up to 1000C.42 It also displayed sloping charge/discharge curves
within a wide potential window of 1.2 to 3 V (vs. Li+/Li), which
was different from conventional battery electrode materials.
Intercalation pseudocapacitance was also found in H2Ti6O13.51
The XRD pattern of Li-intercalated H2Ti6O13 electrodes was
almost the same as that of fresh H2Ti6O13 electrodes, demon-
strating that the Li+ ion intercalation did not result in an obvious
change in the crystalline parameters of H2Ti6O13.
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V2O5 also presented a two-dimensional ion (Li+ and Na+)
diffusion pathway with intercalation pseudocapacitance. Its
open and layered structure enabled fast ion transport within
the V2O5 bulk.52,53 The V2O5 anchored on CNTs displayed a
total charge storage of 2780 C g1 originating from a Faradaic
process and 1855 C g1 from a nonfaradaic process corres-
ponding to charge storage due to surface reactions.52 The
nanocomposites of V2O5/CNT provided facile Na+ ion insertion/
extraction and fast electron transfer, enabling the fabrication
of high-performance Na ion pseudocapacitors in an organic
electrolyte.53 The capacitive processes account for 70% and
95% of the charge storage at 1 mV s1 and 20 mV s1,
respectively. Besides, SnS2 nanosheets, TiO2/graphene and
TiO2/MoO2/C were reported as Na+ ion intercalation pseudo-
capacitive materials, which also displayed both high rate cap-
ability and excellent cycling stability.54–56
3. New materials for supercapacitors
3.1 Metal–organic frameworks
Metal–organic frameworks (MOFs), also known as porous coor-
dination polymers, are receiving increasing attention in the
field of electrochemical energy storage due to their diverse
structures, highly porous frameworks and tunable chemical
compositions which can be designed at the molecular level.57
MOF-derived carbons with various architectures for super-
capacitors were summarized in a recent review.23 Thus, in this
section, only the latest progress on fabricating MOFs directly
for supercapacitors is presented. Note that, MOF-derived carbon
materials, metal oxides, metal sulfides and their composites are
not included here because the inherent properties of these
materials from sacrificial MOF templates do not change as the
electrode for supercapacitors.58,59
MOFs, defined by Yaghi in 1995, are extremely light with
very high specific surface areas (up to 46000 m2 g1), large
pore volumes and well defined pore sizes.60 The entire frame-
work of MOFs is supported by coordination bonds and/or other
weak cooperative interactions such as H-bonding, p–p stacking,
and van der Waals interactions. MOFs can be obtained from
relatively cheap precursors. Inorganic salts (nitrates, sulfates,
and chlorides) are typically applied as the metal-ion precursor.
The organic linkers are usually multidentate organic ligands
such as carboxylates, azoles or nitriles.61 Solvothermal synthesis
is the most frequent method, involving addition of all the
reactants (metal salts, ligands and solvents) in sealed vessels
and then heating at elevated temperatures under subcritical
conditions.62 The microwave-assisted method and surfactant-
assisted synthesis have also been developed for fabricating
MOFs.63,64 Large-scale production of MOFs in tonnes was
achieved by some companies, such as BASF, MOF Technologies
and Strem Chemicals.65 MOFs provide opportunities to tailor
single atomic active metal centers which can reduce the mass
consumption and increase the electrode/electrolyte interface.
The controllable pore size in the micropore range (0.6–2 nm)
and the ability to incorporate pseudo-capacitive redox metal
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centers make MOFs potential candidates as electrode materials
for supercapacitors.
In 2011, the use of MOFs as electrode materials for super-
capacitors was firstly demonstrated employing some Co-based
MOFs in a 1 M LiOH aqueous electrolyte and a 0.1 M TBAPF6
(tetrabutylammonium hexafluorophosphate)/acetonitrile non-
aqueous electrolyte.66,67 Co8-MOF-5 (Zn3.68Co0.32O(BDC)3(DEF)0.75)
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displayed a very low specific capacitance (below 5 F g1) but both
of them presented low loss in capacitance for 1000 cycles in a
0.1 M TBAPF6/acetonitrile electrolyte. However, in an aqueous
electrolyte, the Co based MOF delivers relatively high specific
capacitances (about 200 F g1).66–68 Then, a specific capacitance
of Ni-based MOFs up to 634 F g1 was reported.69 A reversible
redox peak was found in its CV curves in 6 M KOH, where redox
active species should be coordinated to Ni. Then nanocrystals
made from a series of 23 different MOFs were explored as
electrode materials for supercapacitors.70 Zirconium-based
MOFs achieved the highest gravimetric (726 F g1) and aerial
(5.09 mF cm2) capacitances. In general, electrochemical behaviors
in pristine MOFs are mainly dependent on the properties of particle
size, active surface area, pore size distribution, crystallinity and
availability of functional groups for efficient conductivity.
Ni-Based MOFs of similar topology, [Ni(L)(DABCO)0.5], were
tested in a 2 M KOH aqueous electrolyte.71 In such MOFs,
DABCO is 1,4-diazabicyclo[2.2.2]-octane and L is a functionalized
ligand such as NDC (1,4-naphthalenedicarboxylic acid), ADC
(9,10-anthracenedicarboxylic acid), or TM (2,3,5,6-tetramethyl-
1,4-benzenedicarboxylic acid). A Ni–DMOF–ADC based electrode
presented higher specific capacitance and better rate perfor-
mance than the other two. The Ni3(btc)212H2O MOF material,
obtained by adding NiCl26H2O together with H3btc (1,3,5-
benzenetricarboxylic acid) in a solvent of DMF, exhibited super-
ior pseudocapacitive behavior in a KOH aqueous electrolyte with
a high specific capacitance of 726 F g1.72 The asymmetric
supercapacitor achieved a high energy density of 16.5 W h kg1
using this nickel-based MOF as a positive electrode and commer-
cial activated carbon as a negative electrode in KOH electrolyte.
Similarly, another Ni based MOF through mixing NiCl26H2O
and PTA (p-benzenedicarboxylic acid) in DMF (N,N-dimethyl-
formamide) showed a pseudocapacitive behaviour with a couple
of redox peaks at 0.32 and 0.17 V vs. a saturated calomel
electrode (SCE).73 The electrochemical reactions might be repre-
sented by eqn (6):74
[Ni3(OH)2(C8H4O4)2(H2O)4]2H2O + OH  e
2 [Ni3O(OH)(C8H4O4)2(H2O)4]2H2O + H2O. (6)
The (100) plane in such MOFs is the largest exposed facet.
Along the [001] direction, the chains of Ni octahedra with 1D
structure connected to each other can provide a conductive
path for electrons, while the parallel layers with interspaces
along the [010] direction can promote the storage and diffusion
of electrolyte ions. To further improve the capacitance,
Zn-doping was introduced into such MOFs.75 With increasing
Zn content, the capacitance value initially increased, and then
tended to decrease. A maximum specific capacitance of 1620 F g1
6822 | Chem. Soc. Rev., 2017, 46, 6816--6854
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was reached at a rate of 0.25 A g1. The doped Zn2+ ions can
enlarge the interlayer distance providing enough space for
electrolyte ion diffusion and act as a pillar to prevent the
collapse of the crystal ensuring good cycling behaviors.
The poor electron-conductive property of most MOFs
was the biggest disadvantage for them as electrode materials
for supercapacitors. Thus, composites combining MOFs and
carbon-based species (CNT, RGO, and C3N4) were investigated
recently.76–78 Carbon materials are expected to increase the
electronic conductivity and thus enhance charge transfer char-
acteristics. In addition, the conductive MOF, Ni3(2,3,6,7,10,11-
hexaiminotriphenylene)2 (Ni3(HITP)2) with high electronic
conductivity (45000 S m1), served as the free-standing electrode
material in an EDLC without conductive additives or other
binders.79 Ni3(HITP)2 consisted of stacked p-conjugated 2D layers
with an surface area of 630 m2 g1, which were penetrated by 1D
cylindrical channels of B1.5 nm diameter (Fig. 4a). Ni3(HITP)2
powder could be pressed into self-supported pellets at high
pressure with a density of 0.6  0.2 g cm3. In a tetraethylam-
monium tetrafluoroborate/acetonitrile (TEABF/ACN) electrolyte,
galvanostatic charge and discharge of Ni3(HITP)2//Ni3(HITP)2
symmetrical supercapacitors displayed a gravimetric capacitance
of 111 F g1 at the low current density of 0.05 A g1 with
triangular traces (Fig. 4b). The obtained areal capacitance was
18 mF cm2, higher than those observed for most carbon
materials (Fig. 4c). The equivalent series resistance (ESR) of
the Ni3(HITP)2//Ni3(HITP)2 symmetrical supercapacitor was as
low as 0.47 ohm (0.61 ohm cm2). It showed a loss of 10% in
capacitance and no increase in the ESR after 10 000 cycles. When
assembling the Ni3(HITP)2 pellets, increasing the pressure can
Fig. 4 The conductive MOFs as electrode materials for supercapacitors.
(a) Molecular structure of Ni3(HITP)2. (b) Its galvanostatic charge/discharge
curves at various current densities. (c) Comparison of areal capacitances
among various EDLC materials. The areal capacitance for various materials is
normalized relative to their BET surface areas. (d) Relative size of pores,
electrolyte Et4NC and BF4 ions, and acetonitrile solvent molecules shown
in a space-filling diagram of idealized Ni3(HITP)2. Green, lime, blue, grey,
brown, and white spheres represent Ni, F, N, C, B, and H atoms, respectively
(modified from ref. 79, copyright permission from Nature Publishing Group).
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increase the density of the electrodes to 1.1  0.2 g cm3. These

denser pellets gave rise to significantly improved volumetric
capacitances of up to 118 F cm3 with little negative effect on
gravimetric capacitances and the ESR. The large open channels
in Ni3(HITP)2 can enable swift electrolyte movement and reduce
volume changes on repeated charge/discharge cycling. TEA+,
TEA+7ACN, BF4 and BF49ACN exhibit ionic diameters of
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0.68, 1.3, 0.46 and 1.16 nm, respectively, and can fit comfortably
within the one-dimensional channels of Ni3(HITP)2 (Fig. 4d).
Generally, MOFs exhibit both rigid and flexible structures which
can be further tuned to optimize the conductivity.

3.2 Covalent organic frameworks

In 2005, Yaghi and co-workers designed porous organic frame-
Fig. 5 Redox-active moiety modified COFs as electrode materials for
works connected via covalent bonds, which were the first supercapacitors. (a) Synthesis of DAAQ-TFP COF. (b) Cyclic voltammo-
successful examples of the so-called covalent organic frame- grams of DAAQ-TFP COF in a 1 M H2SO4 electrolyte at different scan rates.
works (COFs).80 COFs represent a fascinating new type of covalent (c) The corresponding redox reaction (modified from ref. 91, copyright
porous crystalline polymers enabling the elaborate integration of permission from the American Chemical Society).
organic building blocks into an ordered structure with atomic
precision.81 The formation of strong covalent bonds through
redox processes with a potential at 0.05 V (vs. AgCl/Ag) in a
various synthetic organic reactions between the building units
1 M H2SO4 electrolyte as shown in Fig. 5b.91 DAAQ moieties can
enabled COFs with well-defined and predictable 2D or 3D
be reduced to 9,10-dihydroxyanthracenes upon two-electron,
crystalline structures.82 In COFs, the organic building units
two-proton reduction in a protic electrolyte (Fig. 5c). The peak
are held together by strong covalent bonds, such as B–O, C–N,
separation (DEp) between the oxidative and reductive peaks was
B–N, and B–O–Si.83,84 Similar to MOFs, the COFs have high
only 4 mV s1, suggesting a rapid electron transfer during the
surface areas, controllable pore sizes and highly flexible mole-
redox reaction. Furthermore, the peak current was directly
cular designs. The rapid development in this area has attracted
proportional to the scan rate over the range of 1–1000 mV s1,
increasing interest from scientific researchers in various fields
which was typical of a surface-confined redox couple. The
ranging from organic synthesis to energy storage.85
electrode based on DAB-TFP COF displayed a capacitance of
It is believed that the formation reaction of the COF should
48  10 F g1. After 10 charge/discharge cycles, its capacitance
be a reversible reaction since it is difficult to crystallize linked
was stabilized at 40  9 F g1, which showed no further
organic polymers into solids using irreversible reactions. In the
significant decrease after 5000 cycles. To make full use of the
case of preparation methods of COFs, solvothermal synthesis
redox-active groups in the DAB-TFP COF, oriented thin films
was one of the most common methods. Normally, monomers
were formed through the slow introduction of the DAAQ mono-
and mixed solvents are placed in a Pyrex tube and degassed.
mer into a solution of TFP (1,3,5-triformylphluroglucinol) in the
After that, the tube is sealed and heated to a designated
presence of Au substrates.92 Galvanostatic charge/discharge tests
temperature (ranging between 80 and 120 1C) for a certain
showed that the specific capacitance of the DAAQ-TFP COF was
reaction time (taking 2–9 days). Finally, the precipitate is
drastically improved from 0.4 to 3 mF cm2 by using oriented
collected, washed with suitable solvents, and dried under
crystalline thin films. Such DAAQ-TFP COF thin films provided
vacuum to yield the COF as a solid powder.80,81 To rapidly
near-quantitative addressability of the anthraquinone moieties
and efficiently synthesize COFs, microwave reactions have been
at a thickness of up to B200 nm.
applied under solvothermal conditions, which make large-scale
A pyridine containing COF (TaPa-Py COF) also exhibited rever-
synthesis of COFs possible.86 Besides the solvothermal method,
sible electrochemical processes in a 1 M H2SO4 electrolyte.93 The
the ionothermal method was also applied to produce crystalline
redox behavior of the TaPa-Py COF is from the redox active pyridine
porous COFs.87 A molten ZnCl2 salt at 400 1C acted as the
moieties. During the electrochemical process, pyridine of the
solvent and catalyst for the reversible reaction. One of the
TaPa-Py COF first takes H+ ions and gains an e, forming a
biggest disadvantages in ionothermal synthesis is the poor
pyridinyl radical. In the next successive step, the pyridinyl
crystallinity control because of the harsh reaction conditions.
radical takes another H+ ion and gains an e, changing to
Different from the bulk synthesis, monolayer COFs can grow on
dihydropyridine (DHP) as shown in eqn (7).
the surface of some substrates (such as clean Ag, highly ordered
pyrolytic graphite (HOPG) and graphene).88–90
The poor hydrolytic and oxidative stability of boronate ester- (7)
linked frameworks in early COFs precluded their application
in energy storage. Until 2013, when incorporating redox-active
2,6-diaminoanthraquinone (DAAQ) moieties into a 2D COF A capacitance of 180.5 F g1 for the TaPa-Py COF was obtained
linked by b-ketoenamines (Fig. 5a) resulted in well-defined at 20 mV s1. At a current density of 0.5 A g1, it delivered a

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capacitance of 209 F g1 with a combination of Faradaic
capacitance along with double-layer capacitance originating
from the pyridine units and the ordered porous structure of
the TaPa-Py COF. The symmetrical supercapacitor based on the
TaPa-Py COF showed excellent cycling stability after 6000
charge/discharge cycles with 92% capacitance retention.93 To
enhance the conductivity of 2D COFs, facile electropolymeriza-
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tion of EDOT within the pores of COF films (B1 mm) was
achieved very recently.94 The PEDOT-modified DAAQ-TFP COF
exhibited well-defined redox peaks associated with the reduction
and oxidation of the anthraquinone moieties. It had a higher
capacitance of 197 F g1 than that of the pure DAAQ-TFP COF
and retained more than 80% of its capacitance when charged/
discharged at 10 and 100C. Amazingly, it even retained 50% of
its maximum capacitance at the extremely high charging rate of
1600C corresponding to a charging time of only 2.25 s.
3.3 MXenes
The discovery of graphene opened a gate for exploration of 2D
materials.95–98 MXenes, a recently discovered family of 2D
transition metal carbides and carbonitrides (Nb2C, Ti3C2,
Ta4C3, etc.), have received increasing attention since 2011.99
They consist of Mn+1Xn layers, where M is an early transition
metal, X is carbon and/or nitrogen, and n = 1, 2 or 3. They
exhibits various unique properties (such as high conductivity,
good mechanical properties, and hydrophilicity), making them
quite attractive for energy storage applications. For instance,
Ti3C2-based MXenes displayed an electronic conductivity as
high as 7000 S cm1 depending on the terminating functional
groups on the surface.
MXenes are usually produced by the selective etching of
‘‘A’’ element layers (mostly Al) from the MAX phases via
wet chemistry routes, such as etching in HF,99,100 or acidic
solutions of fluoride salts (LiF in HCl).101 This synthesis yields
electron-conductive MXene layers with –F and –OH/QO surface
termination abbreviated as Tx, thus giving a general formula of
Mn+1XnTx. Among the MXene family, Ti3C2Tx is the most
studied one to date. In situ polymerization of pyrrole confined
between Ti3C2Tx layers was achieved by mixing a Ti3C2Tx
suspension and pyrrole at room temperature at 1000 rpm using
a vacuum filtered process.102 Nb2CTx was obtained by selective
removal of Al from Nb2AlC in an HF solution. It was subse-
quently oxidized in a CO2 atmosphere to synthesize a Nb2O5/
carbon/Nb2CTx composite.103 The oxidation temperature, time,
and CO2 flow rate would determine the Nb2O5 crystal size as
well as the structure, composition, and charge storage proper-
ties of the hybrid material. Sandwich-like MXene/CNT compo-
site paper electrodes were fabricated by alternating filtration of
MXene and CNT dispersions.104 At first, a thin layer of MXene
flakes was formed by vacuum-assisted filtration of the solution
containing Ti3C2Tx flakes. After that, a layer of CNT was
deposited on top. Such processes were repeated several times
to obtain composite paper electrodes. Films several micro-
meters in thickness could be fabricated in 10 minutes, which
was much simpler, faster, and more effective than the conven-
tional layer-by-layer (LBL) assembly processes.
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In 2013, the initial study of Ti3C2Tx as an electrode material in
supercapacitors showed capacities of 50–100 F g1 for intercala-
tion of cations such as Li+, Mg2+ or Al3+ in aqueous electrolytes.
Because of the low tap density of carbon (o0.5–1 g cm3), the
volumetric capacitance of carbon-based electrodes is usually
limited below 300 F cm3. Impressively high volumetric capaci-
tance reaching 900 F cm3 was measured for Ti3C2Tx in aqueous
electrolytes, which was comparable with hydrated RuO2.101
Spontaneous cation intercalation accompanied by electrode
deformations (expansion/contraction) was evidenced by electro-
chemical quartz crystal admittance (EQCA)105 and in situ X-ray
absorption spectroscopy106 studies of Ti3C2Tx multilayer parti-
cles in several aqueous electrolytes with different cations.
Similar to other 2D materials, the restacking of MXene
flakes during production limits the accessibility to electrolyte
ions, and hinders the full utilization of their surfaces. By
separating multilayer stacks into few-layered sheets, the energy
storage properties of MXene were enhanced and the area of the
electrochemically active surface could be increased.107 Another
effective strategy for improving the electrochemical perfor-
mance of MXene was to introduce interlayer spacers. The
hydrazine treated Ti3C2-based MXene demonstrated a greatly
improved capacitance of 250 F g1 in acidic electrolytes with an
excellent cycling stability even if the MXene electrode was as
thick as 75 mm.108 Besides creating a pillaring effect between
Ti3C2Tx layers improving the accessibility to active sites, the
hydrazine intercalation into 2D titanium carbide led to changes
in its surface chemistry by decreasing the amount of –F, and
–OH surface groups and intercalated water. In addition, inter-
calation of polymers (such as polypyrrole and polyvinyl alcohol)
also facilitated charge transport in supercapacitor electrodes.102,109
For example, Ti3C2Tx MXene was mixed with either a charged
polydiallyldimethylammonium chloride (PDDA) or an electrically
neutral polyvinyl alcohol (PVA) to produce flexible free-standing
Ti3C2Tx/polymer films (Fig. 6a). PDDA is a cationic polymer while
the Ti3C2Tx flakes are negatively charged. PVA has good solubi-
lity in water and a large concentration of hydroxyl groups along
its backbone. The as-fabricated composites were flexible and
have high electronic conductivities. The tensile strength of the
Ti3C2Tx/PVA composites was significantly improved compared
with pure Ti3C2Tx or PVA films. The intercalation and confine-
ment of the polymer between the MXene flakes not only
increased flexibility but also enhanced cationic intercalation
of the MXene/PVA composite film.109 Besides, the PPy/Ti3C2Tx
composite exhibited a high gravimetric capacitance (416 F g1)
with an excellent cycling stability up to 25 000 cycles.102
Although the density of the MXene composite paper electrodes
decreased slightly with the incorporation of the CNTs, higher
volumetric capacitances were still obtained for the sandwich-
like MXene/CNT composite.104 A high volumetric capacitance
of 435 F cm3 was obtained at 2 mV s1 for such a sandwich-
like composite. When the scan rate increased to 200 mV s1, a
capacitance of 320 F cm3 was achieved. It yielded a volumetric
capacitance of around 300 F cm3 at 10 A g1, which increased
to 350 F cm3 after 10 000 cycles. The gradual increase with
cycling may result from the gradual electrolyte wetting between
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Fig. 6 Polymer modified MXene and in situ XRD study on the mechanism
of MXene during the charge/discharge process. (a) A schematic illustration
of MXene-based functional films (modified from ref. 109, copyright per-
mission from National Academy of Sciences USA). (b) Electrochemical
in situ X-ray diffraction study of Ti3C2Tx film at various constant potentials
(0.5 V steps) in an EMI-TFSI electrolyte. Green squares represent peaks of
the in situ XRD cell without working electrodes (modified from ref. 112,
copyright permission from Elsevier).
MXene flakes during cycling. Interestingly, terminal fluorine
was successfully replaced with oxygen-containing functional
groups after the chemical intercalation of potassium salts.110
This change in surface chemistry led to a 4-fold increase in the
capacitance in sulfuric acid solution.
Considering all the above discussions, MXenes and their
composites have shown excellent volumetric capacitance in
aqueous electrolytes, but displayed limited electrochemical
windows due to water electrolysis. Thus the electrochemical
behaviors of Ti3C2Tx in organic and ionic liquid electrolytes
were investigated.111 In a 1 M solution of 1-ethly-3-methylimid-
azolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) in aceto-
nitrile, a Ti3C2Tx/CNT electrode displayed capacitances of
85 F g1 and 245 F cm3 at 2 mV s1. In situ X-ray diffraction
study reveals the intercalation of large EMI+ cations into the
MXene. Very recently, electrochemical characteristics of Ti3C2Tx
electrodes were investigated in a neat EMI-TFSI electrolyte.112
As shown in Fig. 6b, when the applied potential increased from
0 V to 1.5 V, a progressive shift of the Ti3C2Tx(00l) peaks to
higher 2y values was observed, indicating a continuous decrease
of the interlayer spacing. When discharging from 1.5 V back to
0 V, those peaks reversibly shifted back to the original position.
In the positive potential range, the decreasing of the interlayer
spacing is due to the electrostatic attraction between intercalated
TFSI anions and positively charged MXene layers and/or
steric effects originating from de-intercalation of EMI+ cations.
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With a decrease of the applied potential from 0.5 V to 2 V,
the XRD peaks of Ti3C2Tx shifted to lower 2y values and the
peak intensity of the (002) peak increases. The expansion of the
interlayer spacing should result from the steric effect caused by
EMI+ cation intercalation. While the appearance of the (002)
peak at a lower 2y degree position can be ascribed to the
pillared structure of Ti3C2Tx flakes after being intercalated by
EMI+ cations. Full charging to 0 V led to the recovery of the
(002) peak, suggesting a reversible transition during the charge/
discharge process.112
The Nb2O5/C/Nb2CTx composite displayed a high capaci-
tance of 660 mF cm2 (275 F g1) over charge/discharge times
of 4 min in a 1 M LiClO4 organic electrolyte.103 Such electrodes
were 50 mm in thickness and 2.4 mg cm2 in mass loading,
which were comparable to commercial devices. The good electro-
chemical performance was attributed to the fast pseudocapacitive
responses of Nb2O5, the high electronic conductivity of Nb2CTx,
and the fast charge transfer pathways provided by the disordered
carbon. Beyond single electrodes and half-cell studies, three
types of Li ion capacitors (full cells) based on Nb2CTx were
investigated recently.113 The Nb2CTx/CNT film electrode can be
paired with either a battery-type negative electrode (graphite)
or a battery-type positive electrode (LiFePO4). All these Li
ion capacitors were capable of operating within 3 V voltage
windows with distorted charge/discharge profiles resembling a
classical triangular capacitive shape. More details about Li ion
capacitors will be discussed in Section 4.4.1.
3.4 Metal nitrides
Metal nitrides (MN, M = V, Ti, W, Mo, Nb, and Ga) have
attracted increasing attention as suitable electrode materials
for high-performance supercapacitors because of their high
electronic conductivities. The most common method applied
to synthesize VN was to use nitride vanadium-based precursors
under a NH3 atmosphere.114–118 In a NH3 atmosphere, the
Ni1xVxO2 binary metal oxide was successfully transformed
into cubic phased VN and metallic Ni, due to the nitridation
effect of ammonia to vanadium oxide and the thermoreduction
reaction between the nickel species and NH3.119 The metallic Ni
was well dispersed in the VN skeleton, enabling good electrical
contact and transfer of the interface electrons. VN could also be
synthesized from the melamine reduction of V2O5 xerogel
under a N2 atmosphere.120,121 Similar to VN, the TiN and WN
were produced by direct thermal nitridation of TiO2122–124 and
WO3125 in NH3, respectively. This process was carried out at a
high temperature (600–1000 1C) for a long period of time. The
used precursors always suffer from serious morphological
changes during the high-temperature and long annealing
processes. Alternative methods were developed, involved in
directly growing or depositing active materials onto substrates
or collectors. For example, TiN nanotubes were synthesized
by atomic layer deposition using tetrakis(dimethylamino)-
titanium(IV) (TDMAT) (or TiCl4) and ammonia (NH3) as the two
precursors.126,127
MoNx and NbNx nanocrystallines were reported to be synthe-
sized through ammonolysis and nitridation of the corresponding
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metal chlorides.128,129 Reactions of MoCl5 or Mo(NMe2)4 with
ammonia followed by pyrolysis of the resultant precipitates
result in g- or d-MoNx.129 Besides, n-type GaN was produced by
metal–organic chemical vapor deposition. To increase its spe-
cific surface area, a single-crystal GaN mesoporous membrane
was successfully fabricated by electrochemical etching.130
A free-standing film of graphite paper/GaN nanowires was
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prepared via the growth of GaN on graphite paper through
catalyst assisted CVD.131 Nanostructured Fe2N on vertically
aligned graphene nanosheets was obtained by atomic layer
deposition (ALD) and thermal annealing in a NH3 atmosphere.132
Thin films of ZnO with a thickness of 20 nm were coated by
ALD onto the graphene nanosheet substrates. ZnO was then
transferred to FeOOH via a solution reaction in 0.5 M Fe(NO3)3.
The FeOOH thin film was finally converted to Fe2N nano-
particles dispersed uniformly on the surface of graphene
nanosheets after ammonia annealing.
The VN electrode materials have notable advantages, such as
large theoretical capacity (41000 F g1), metallic electronic
conductivity, reversible and fast redox Faradic response with
various oxidation states (II–V) of vanadium, and high hydrogen
evolution overpotential.114–116 The specific capacitances of VN
were determined to be 114, 45.7 and 273 F g1 in 0.5 M H2SO4,
2.0 M NaNO3 and 1.0 M KOH solutions, respectively.120
Thus, the KOH solution was considered as the best aqueous
electrolyte for the capacitive performance of VN. In fact, MN
(M = V, or Ti) was one promising candidate for negative
electrode materials in hybrid supercapacitors in alkaline
electrolytes.117–119,121 It was recognized that an oxide layer
was usually presented on the VN surface. One possible reaction
of VN in an aqueous KOH electrolyte was proposed as
eqn (8):119
VNxOy + OH 2 VNxOy//OH + VNxOy–OH, (8)

where VNxOy//OH and VNxOy–OH correspond to the electrical
double layer and redox pseudocapacitance. Recently, it was
found that VN was not very stable in aqueous solution due to
the irreversible electrochemical oxidation reaction of forming
soluble vanadium oxide (VOx) on the surface.117 The stability of
the VN as a negative electrode was significantly improved by
using a LiCl/PVA gel electrolyte.117 The VN nanowire electrode
exhibited a remarkably good cycling stability in the LiCl/PVA gel
electrolyte with a capacitance retention of 95.3% after 10 000
cycles, which was much better than that obtained in a 5 M LiCl
aqueous electrolyte (only 14.1%).117 The charge storage mecha-
nism of VN depended on the nature of the electrolyte, and only
double layer capacitance was observed when using NEt4BF4
solution in acetonitrile as an electrolyte.133 But the specific
capacitance in NEt4BF4/acetonitrile solution was several orders
of magnitude lower than that in the KOH aqueous electrolyte.
The rate capability of porous carbon can be tuned by coating
TiN on the surface. C@TiN maintained a rectangular shape very
well in its CV curves even at 500 mV s1.122 The TiN coating
significantly improved the kinetic response of the electrode
although some TiO2 and TiON phases were formed on the surface
of the TiN nanocrystallites.122,127 In an aqueous electrolyte, the
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TiN electrode is not very stable because of some irreversible
electrochemical reactions as shown in eqn (9) and (10):
TiN + 2H2O - TiO2 + 0.5N2 + 4H+ + 4e, (9)
2TiN + O2 - TiO2 + N2. (10)
In this regard, MnO2 deposition,126 and polymer and carbon
coating techniques124,127,134 gave improved long-term cycling
stability compared to the bare TiN electrode.
The electrochemical behavior of WN was studied in various
aqueous electrolytes including 1 M H2SO4, 1 M KOH, 3 M KCl,
3 M NaCl, 1 M LiCl and 1 M CaCl2.125 The highest specific
capacitance was observed in a 1 M KOH electrolyte. Similarly, in
the 1 M KOH electrolyte, the highest capacitances for NbN and
g-Mo2N crystallites were 73.5 F g1 and 111 F g1, respectively,
at a scan rate of 2 mV s1.128 But their electrochemical stability
windows were rather narrow, ranging from 1.0 to 0.7 V
for NbN and 1.1 to 0.2 V for g-Mo2N with respect to the
Hg/HgO reference electrode. Differently, in aqueous H2SO4 or
K2SO4 electrolytes within the potential range of 0.7 to 0 V
(vs. Hg/HgSO4), pseudocapacitance took a much more promi-
nent role in the distorted rocksalt structure of imide-derived
Mo2N while the effect of double layer capacitance was more
significant in the chloroimide-derived Mo2N.129
When a GaN mesoporous membrane was utilized as an electrode
for supercapacitors, the capacitance ranged from 23.11 mF cm2
at 0.5 mA cm2 to 12.86 mF cm2 at 100 mA cm2.130 It was
demonstrated that the metal oxynitride thin films could
enhance the pseudocapacitance of GaN in acid electrolytes
as per eqn (11):
GaN1xOx + 2yH+ + 2y e 2 GaN1xyOxy + yH2O. (11)
The flexible supercapacitor based on GaN nanowire/graphite
paper nanocomposites manifested a high specific capacitance
of 53.2 mF cm2, and high energy and power densities
(0.30 mW h cm3 and 1000 mW cm3).131 The outstanding
electronic conductivities of the GaN nanowire (6.36  102 S m1)
and graphite paper (7.5  104 S m1) delivered a synergistically
enhanced electrochemical performance.
3.5 Black phosphorus
An increasing number of monolayer/multilayer 2D nanomaterials
(such as hexagonal boron nitride, transition–metal dichalco-
genides, 2D COFs and 2D MOFs) with various unique physical
and chemical properties have been widely studied in various
applications. Among the large family of 2D nanomaterials,
black phosphorus (BP) is attracting enormous attention because
of its distinct structure with corrugated planes of P atoms, which
are connected by strong intralayer P–P bonding and weak
interlayer van der Waals forces.135 By breaking down the weak
interlayer interactions, the bulk BP can be exfoliated into thin BP
sheets with a few layers or even a monolayer.136
Few-layer BP (also called phosphorene) has a direct band gap
which can be tunable between 0.30 and 2.2 eV by controlling
the number of layers. Moreover, BP has a large spacing of 5.3 Å
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between adjacent puckered layers, larger than the 3.6 Å of
graphite and comparable to the 6.15 Å of the 1T MoS2
phase.137 Similar to the other 2D materials, BP nanosheets
were utilized as electrode materials and a polysulfide immobi-
lizer in rechargeable batteries, like Li or Na ion batteries138,139
and Li–S batteries.140 The exploration of BP in supercapacitors
is still very much in its infancy.137 There are several methods
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to produce BP crystals, such as using high-energy mechanical
ball-milling of red phosphorus, heating toxic white or red
phosphorus under high pressure or transforming white phos-
phorus in liquid metal.140 To obtain few-layer phosphorene
nanosheets, a liquid exfoliation approach in organic solvents
(such as acetone and N-methyl-2-pyrrolidone) is the most
common method.137,140
A flexible all-solid-state supercapacitor was demonstrated in
a PVA/H3PO4 gel electrolyte with liquid-exfoliated BP nano-
flakes as flexible electrodes.137 It displayed volumetric capaci-
tances of 17.78 F cm3 (59.3 F g1), 13.75 F cm3 (48.5 F g1)
and 4.25 F cm3 (14.2 F g1) at scan rates of 0.005, 0.01 and
0.09 V s1. The capacitive retention was 71.8% after 30 000 cycles. It
showed an energy density ranging from 0.123 to 2.47 mW h cm3
and a maximum power density of 8.83 W cm3. Normally, the
diffusion of water to BP nanoflakes can lead to an irreversible
reaction between water and phosphorus. Interestingly, such a
reaction on liquid-exfoliated BP nanoflakes was able to produce
complicated oxygen functional groups (like POx) owing to
the contaminated surfaces with molecules of solvent. These
produced oxygen functional groups on the surfaces of BP
nanoflakes may serve as reversible adsorption/desorption sites
of H+ ions, which is beneficial for significant enhancement of
specific capacitances. Moreover, the presence of oxygen func-
tional groups and H3PO4 on the surfaces of BP nanoflakes can
efficiently prevent the direct contact between the diffused water
and BP nanoflakes, thus reducing the reaction-induced damage
of the BP nanoflakes.
3.6 Other materials
Due to its low cost and environmental friendliness, and the
abundance of manganese resources, spinel LiMn2O4 is regarded
as one of the most promising positive electrode materials for Li
ion batteries.141–143 Its kinetics of charge storage are controlled
by the diffusion of Li ions within the LiMn2O4 structure, which is
not suitable for supercapacitors. Interestingly, intercalation
pseudocapacitance has been reported in a nonstoichiometric
LixMn2O4 (1 o x o 2) mesoporous thin film by Dunn’s group
very recently.144 The nanoporous Mn3O4 films were converted to
nanoporous LixMn2O4 (1 o x o 2) via solid-state reaction with
LiOH calcined at 500 1C in air. The working electrode using
nanoporous LixMn2O4 (1 o x o 2) films deposited on the ITO
substrates presented a reversible capacity of 55 mA h g1 at a
sweep rate of 10 mV s1 (corresponding to a charging time of
2 min).144 In stoichiometric LiMn2O4, its theoretical capacity was
148 mA h g1 with Li ion extraction occurring at approximately
4 V (vs. Li+/Li) in a two-stage process (LiMn2O4/Li0.5Mn2O4 and
Li0.5Mn2O4/l-MnO2). The low capacity of nanoporous LixMn2O4
was due to the fact that the surface of the nanoporous LixMn2O4,
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which should contain exclusively Mn3/4+, presented a spinel
structure with reduced Mn2+ (inactive) in the tetrahedral
site. But even at 1000C, it still displayed a reversibly capacity of
20 mA h g1 corresponding to 0.1 mol of lithium per mole of
LixMn2O4. According to the relationship between current and
sweep rate, the majority of the charge storage in nanoporous
LixMn2O4 arose from pseudocapacitive mechanisms and not
from electric double-layer capacitance. The small wall thickness
(15 nm) ensures that the majority of the lithium in this material
is located in ‘‘near-surface’’ sites. At 10 mV s1, the separation
between the anodic and cathodic peak potentials was less than
0.059 V. Such high electrochemical reversibility indicates there
was relatively little structural change upon lithiation and
delithiation.144 Actually, as early as three years ago, Wu’s group
reported nonstoichiometric LixMn2O4 (0.5 o x o 1) with a nano-
porous structure as the electrode for aqueous supercapacitors.145a
The nanoporous LiMn2O4 spinel was prepared by a hydro-
thermal method using MnO2 nanotubes as a precursor at
180 1C. Presumably due to the low reaction temperature, Li+ ions
could not fully penetrate into the interior of MnO2 to form
LiMn2O4 and some amounts of phase impurities are present in
the sample. It exhibited a specific capacitance of 189 F g1
(about 63 mA h g1) at 0.3 A g1. A stable specific capacitance
of 166 F g1 (55 mA h g1) could be achieved when the current
rate was increased to 12 A g1. After 1500 cycles, there was no
evident capacity fading.145a Generally, the use of nanoparticles or
wires alone cannot solve the diffusion problem unless each
individual nanoparticle or nanowire can be exposed to the liquid
electrolyte. Nanocrystal-based nanoporous materials can create
this ideal architecture, thus bringing intercalation pseudocapaci-
tance. In addition, other MxMnO2 (M = Na and K) materials have
been applied as electrode materials for supercapacitors.145b–d The
sizes of Na+ and K+ are larger than that of Li+ and the structure of
MxMnO2 (M = Na and K) was not spinel but instead layered. Small
redox couples were found in the CV curves of MxMnO2 (M = Na
and K), indicative of pseudocapacitance properties, which were
ascribed to the intercalation/de-intercalation of Na+ and/or K+ into
and from the solid lattice near the surface of the bulk.145b,c
Mixed conductors, composed of purely electronic conductors
and purely ionic conductors, exhibit varied stoichiometries,
giving them substantial potential for use as electrodes.146 Very
recently, Maier and co-authors reported a milestone work on
composites of RbAg4I5/graphite as artificial mixed conductors
for all-solid-state supercapacitors.147 In pure ionic conductors
(like RbAg4I5) or pure electronic conductors (like graphite), the
stoichiometry changes were impossible due to the lack of one
necessary carrier and the high electronic energy. While the
heterogeneous mixed conductor (RbAg4I5/graphite) can quickly
take up or release substantial silver with excess and deficiency.
As shown in Fig. 7a, the silver deficiency was realized by
 0 
vacancies VAg on the ionic-conductor (RbAg4I5) side and
electron holes (h ) on the electronic-conductor (graphite) side.
The silver excess was realized by silver interstitials (AgI ) on one
side and excess electrons (e 0 ) on the other side. Furthermore,
the super-ionic conductor (RbAg4I5) can naturally be utilized as
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Fig. 7 Mixed conductors as electrode materials for supercapacitors.
(a) Schematic of Ag deficiency and excess through interfacial storage.
(b) Schematic illustration of the all-solid-state supercapacitor based on
RbAg4I5/graphite. (c) The frequency dependence of the real (C 0 ) and
imaginary (C00 ) parts of the capacitance (modified from ref. 147, copyright
permission from Nature Publishing Group).
a solid electrolyte (Fig. 7b). Such all-solid-state supercapacitors
had specific capacitances ranging from 0.06 to 0.09 F cm3 with
an extremely short relaxation time (t0) of 40 ms (Fig. 7c).
Recently LaMnO3 nanoparticles as electrode materials for
supercapacitors have been prepared via a reverse-phase hydrolysis
method.148 Ideal LaMnO3 shows a cubic perovskite structure,
where lanthanum atoms locate at a body centered position,
manganese atoms at cubic corner positions, and oxygen atoms
at mid-edge positions. It was found that oxygen intercalation had
a significant effect on LaMnO3 perovskite nanoparticles as super-
capacitor electrodes. The specific capacitances of LaMnO3.09 and
LaMnO2.91 reached 586 and 609 F g1, respectively. Interestingly,
oxygen intercalation was the major charge storage mechanism of
LaMnO3 perovskite supercapacitor electrodes. This assumption
was further demonstrated by applying an electrolyte with varying
anion concentrations as well as different electrolyte types
(i.e. neutral and alkaline electrolytes). The diffusion rate of
O2 in LaMnO3.09 was approximated as 5.6  1012 cm2 s1.
The diffusion rate doubled to 1.2  1011 cm2 s1 in LaMnO2.91
with the introduction of oxygen vacancies.148 Perovskite materials
might open a new paradigm as supercapacitor electrode materials
for oxygen-ion-based charge storage.
4. New devices for supercapacitors
4.1 Flow supercapacitors
The redox flow batteries are one of the most suitable candidates
for large-scale energy storage in the grid because their energy
densities are dependent on the volumes and concentrations of
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the electrolytes, and the power densities can be made flexible by
altering the size of the stack and the number of single cells.149–151
In 2012, researchers demonstrated that supercapacitors could be
scaled up for grid energy storage applications through the
utilization of flowable carbon slurry in electrolytes for capacitive
energy storage, which was called flow supercapacitors or electro-
chemical flow capacitors.152–154 Fig. 8 shows the flow-assisted
supercapacitor device based on suspension electrodes. Different
from redox flow batteries with two primary storage tanks contain-
ing two redox-electrolytes, flow supercapacitors are characterized
by four tanks. During the charging process, the slurry electrode is
pumped through a polarized flow cell, where energy storage
occurs through the formation of the EDLC at the surface of the
carbon particles. When the particles are charged, the presence
of counter ions and co-ions at the surface makes the particles
(and suspension) electrically neutral. Ion diffusion from one
slurry electrode to another occurs through a low cost porous
separator (e.g., polyvinylidene fluoride membrane) that acts as
an electrical insulator. Once charged, the slurry is pumped into
an external reservoir for storage. From these reservoirs, the
slurry can be pumped back into the electrochemical cell, where
the material can be fully discharged for energy recovery.
The flow supercapacitors have the advantages of both super-
capacitors and flow batteries; namely the high power density
and long cycle lifetime of supercapacitors and the scalable
energy of flow batteries. Thus, they are targeted for high-
power applications on the grid. But two disadvantages of flow
supercapacitors are: (1) electrochemical inefficiencies due to
charge leakage outside the electroactive region and (2) charge
redistribution as a result of a non-uniform flow profile. A synergistic
balance between the flow-properties and suspension-electrode
design played a pivotal role in overcoming polarization challenges
and promoting efficient utilization of the active material in a
suspension electrode.154 A suspension electrode, which is the core
of flow supercapacitors, normally includes an electrochemically
active solid material, a conductive additive and an electrolyte.
Spherical activated carbons and non-spherical titanium carbide
were first examined as the active material for the flow super-
capacitor, which displayed a capacitance of 125 F g1 in aqueous
electrolytes and 49 F g1 in organic electrolytes.152 The flowable
electrode composed of carbon spheres activated at 1000 1C for one
hour showed significantly enhanced performance both in static
and under intermittent flow conditions.155 The effects of
the solid fraction, shape, and size of the carbon particles on
the electrochemical and rheological properties of the slurry
electrodes were then investigated.156 Carbon bead slurries
containing intermediate-sized spherical particles presented
the highest capacitances and rate capabilities due to improved
percolation through the particle network, increased surface
area and more favorable diffusion of ions through the pore-
structure of the particles. Highly porous carbon spheres with a
submicrometer size were obtained by using a modified Stober
method followed by carbonization and activation steps.157 When
applied as a capacitive flowable suspension electrode, they
offered shorter transport pathways for facile ion and charge
transport compared with the micron size carbon spheres.
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Fig. 8 Schematic illustration of the flow supercapacitor. Slurry electrode
is the core of a flow supercapacitor. Ion diffusion from one slurry electrode
to another occurs during the charging/discharging process.
Graphene and its composite based suspension electrodes
were examined in flow supercapacitors recently.158,159 The flow
supercapacitor based on a graphene nanoplatelet slurry showed
a capacitance of 1.08 F and 2 V device performances with a
slurry input of 24 mL.158 The energy density and power density
were 0.064 W h L1 and 0.013 W L1, respectively, which were
better than those with a graphite slurry (0.02 W h L1 and
0.004 W L1). The nanosize of graphene helps in the improve-
ment of energy storage and hence the capacitance. The hybrid
suspension electrode of RGO and micron-sized carbon spheres
(CS) with a 1 : 2 (GO : CS) ratio gave the highest gravimetric
capacitance (200 F g1) and the lowest equivalent series resis-
tance (ESR) value.159 It should be noted that the higher amount
of RGO (1 : 1, GO : CS) led to a higher viscosity (poor flowability),
poor rate capability, and lower gravimetric capacitance.
Interestingly, redox-active species (like hydroquinone160,161
and p-phenylenediamine162) were introduced into the carbon
slurries for increasing the overall capacitance and energy of
flow supercapacitors. A flowable electrode composed of hydro-
quinone/carbon spheres under intermittent flow conditions
yielded a capacitance of 64 F g1, which is 50% higher than that
of the flowable electrodes based on pristine carbon spheres.160
The hydroquinone molecules could be either deposited on
carbon spheres by a self-assembly approach or utilized as a
redox-mediating agent in the electrolyte. p-Phenylenediamine
(PPD) as a redox mediator was also shown to dramatically
enhance the capacitance of flow supercapacitors.162 The redox
couple p-phenylenediamine and p-phenylenediimine (PPD/PPI)
is a two-electron and two-proton transfer reaction with pseudo-
capacitive behavior. More discussion on redox couples used in
supercapacitors will be found in Section 4.3.
The employment of an asymmetric configuration was another
strategy to improve the energy density of flow supercapacitors.163–165
An expanded voltage window of 1.6–1.8 V was achieved when
combining a composite of a MnO2–carbon suspension (positive
electrode) and an activated carbon suspension (negative electrode)
in a charge balanced asymmetric device.163,164 The expansion
of the voltage window resulted in a significant increase in the
energy density to above 10 W h kg1, which was 3 times higher
than that of a symmetric suspension electrode based on
activated carbon. A record energy density (20.9 W h kg1) was
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achieved for aqueous flow Li ion capacitors employing high-
performance Li-insertion-type electrode materials (LiMn2O4) and
activated carbon slurry electrodes.165 More information and
discussion on Li ion capacitors will be presented in Section 4.4.1.
4.2 Alternating current (AC) line-filtering supercapacitors
Alternating current (AC) electricity is normally generated at
a frequency of 60 Hz. Higher-order harmonics (typically
4120 Hz) can be induced when nonlinear loads are connected
in the circuitry, which are detrimental to the electronic devices.
AC line-filters are widely applied to smoothen the leftover AC
ripples for the operation of most line-powered electronics.
Currently, commercialized aluminum electrolytic capacitors
(AECs) are utilized for this purpose but with low specific
capacitances. Their bulky volume makes them usually the largest
components in electronic circuits, which is incompatible with the
rapid development of miniaturized and wearable electronics.
Ultrahigh-rate capacitors need to respond harmonically at 120 Hz
(double the value of the AC frequency, 60 Hz, the United States
standard) to smoothen the leftover AC ripples.166–170 However,
due to the slow and lossy internal response of the polarization,
the phase angle for commercial supercapacitors at 120 Hz is
close to 01, which is far from the 901 value needed for filtering.
When driven by 120 Hz AC, they respond like a transmission line
and behave like a resistor rather than a capacitor. Thus, super-
capacitors with a rate-performance comparable to that of AECs
are expected to be next-generation AC line-filters. Actually, great
progress on AC line-filtering supercapacitors has been achieved
as summarized in Table 1.
The phase angle at 120 Hz can be used as a ‘‘factor of merit’’
to measure AC line-filtering performance. The measured total
resistances at 120 Hz yield the resistor–capacitor (RC) time
constants (tRC). The RC time constants are the results of charge
mobility limitations, electronic and ionic, which appear as
compounded resistance in series with the main capacitance. The
RC time constant can be obtained by the equation tRC = C  Z0 ,
where Z 0 is the resistance derived from the real part of the
impedance (O). And C is the device capacitance calculated from
the equation C = 1/(2pf Z00 ), where f is the frequency (Hz) and
Z00 is the imaginary part of the impedance (O). The relaxation
time constant (t0 = 1/f0) is the minimum time needed to
discharge all the energy from the device with an efficiency of
more than 50%. The characteristic frequency f0 is the value at
the phase angle of 451. A lower t will lead to higher scan rate
ability (Fig. 9a). A phase angle close to 901 in the Bode plot
represents the ability to maintain a capacitive behavior at
high frequencies, which depends also on the time constant t
(Fig. 9b). The typical resistor–capacitor (RC) time constant for
an EDLC is B1 s, which is far too long to be useful for the
common application of 120 Hz filtering (8.3 ms).7a
The supercapacitor based on vertically oriented graphene
nanosheets,166–168 3D graphene169–171 and their composites172
were fabricated with comparable rate performance to those of
AECs. The impedance phase angles of vertical graphene and
activated carbon based supercapacitors and AECs at different
frequencies are plotted in Fig. 9c. The impedance phase angle
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Table 1 Some characteristics of AC line-filtering supercapacitors

Electrode materials Electrolyte Phase at 120 Hz (1) tRC (ms) t0 (ms) Specific capacitance at 120 Hz Ref.
Vertically graphene KOH 82 0.2 — 175 mF 166
Vertically graphene KOH 85 — — 265 mF cm2 167
Vertically graphene KOH E90 — 32.8 30 F g1 168
3D RGO KOH 84 1.35 0.17 283 mF cm2 169
Graphene films H2SO4 — — 13.3 125 F g1 170
0.32 mF cm2
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RGO aerogel — 75.4 0.35 1.9 171

Graphene@CNT Na2SO4 81.5 0.19 0.82 662 mF cm2 172
CNT film TEABF4 84.3 — 0.124 104 mF cm2 173
Porous C film@CNT K2SO4 81 0.2 — 601 mF cm2 174
Carbon sponges KOH 78 0.32 0.37 172 mF cm2 175
PEDOT@graphene H2SO4/PVA E75 0.46 1 75 mF 176
PEDOT H2SO4/PVA 65 0.8 3.3 — 177
PEDOT@PPS H2SO4 84 0.15 0.59 994 mF cm2 178

volumetric energy densities at 120 Hz. The ions in the organic

Fig. 9 The relaxation time, phase angle and frequency for AC line-filtering
supercapacitors. (a) Calculated CV curves of normalized current (I/sC)
versus the voltage, where I is the current, s is the scan rate, and C is
the capacitance. All the CVs are compared for the same scan rates.
(b) Simulation of the impedance phase angle versus frequency with
decreasing t0 (modified from ref. 7a, copyright permission from Nature
Publishing Group). (c) Plot of impedance phase angle versus frequency for
the vertically oriented graphene nanosheet based supercapacitors. (d) Plot
of its specific capacitance versus frequency using a series-RC circuit
model (modified from ref. 156, copyright permission from AAAS).
of the vertical graphene based supercapacitor reached 451 at
B15 000 Hz, and this frequency was much higher than that of
activated carbon based supercapacitors (0.15 Hz) but lower
than that of AEC (B30 000 Hz). The impedance phase angle
of the vertical graphene based supercapacitor was as large
as 821 at 120 Hz (as compared with 01 for the activated carbon
based supercapacitor), which was comparable to that of a
commercial AEC. Capacitance versus frequency is plotted in
Fig. 9d. At 120 Hz, the derived capacitance value was 175 mF,
and the measured resistance was 1.1 O, yielding an RC time
constant of less than 200 ms.166
The structure of CNTs was controlled to be open so that ion
diffusion was sufficiently fast for 120 Hz applications.173,174
Ultrathin CNT films on Au/Ti/Al current collectors in organic
electrolytes enabled AC-line-filtering supercapacitors with high
electrolytes moved sufficiently fast due to the short pore length
of the ultrathin CNT films. In addition, the Au insertion layer
between the CNTs and the current collector greatly improved
the quality of the electrical interfacing and enables the fast
response required for AC line filtering.173 Supercapacitors
based on meso/macroporous camphor-derived carbon sponges
also showed highly promising performance in AC line-filtering,
exhibiting a phase angle of 781 and a RC time constant
of 319 ms at 120 Hz.175 Some surface functional groups (–OH,
–C–O, –CQO) were usually presented on the carbon sponge
surfaces. Those functional groups can improve the electrode
wettability in aqueous electrolytes, resulting in higher ion
mobility and faster ion transport.
Polyethylenedioxythiophene (PEDOT) on different current
collectors (Au/Ti and graphite) was employed to fabricate
flexible supercapacitors for AC line-filtering.176–178 Ultrathin
printable supercapacitors based on PEDOT/graphene could be
operated at an ultrahigh rate of up to 2000 V s1 with an
extremely short RC time constant of less than 0.5 ms.176 The
PEDOT based micro-supercapacitors exhibited excellent frequency
response characteristics (an impedance phase angle of 651
at 120 Hz, a frequency of 400 Hz at a phase angle of 451, t0 of
3.3 ms and tRC of 0.8 ms).177 More discussions on micro-
supercapacitors will be presented in Section 4.5. Instead of
using Au as a current collector, an AC line-filtering super-
capacitor was achieved based on poly(3,4-ethylenedioxythiophene):
poly(styrenesulfonate) (PEDOT:PSS) as an electrode material
and graphite foil as the current collector.178 It exhibited high
areal (994 mF cm2) and volumetric (16.6 F cm3) specific
capacitances at 120 Hz, which were superior to those of the
state-of-the-art supercapacitors for this purpose.
4.3 Redox electrolyte enhanced supercapacitors
Integrating solvated redox-active species into electrolytes has
emerged as an effective strategy to increase the energy density
of EDLCs.179,180 Normally, ion diffusivity is typically around
several orders of magnitude higher in liquids than in solids.
Actually, dissolved redox species react with the same fast kinetics
as the electrostatic surface storage mechanisms. A number of
redox couples have been studied in redox-active electrolyte

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Fig. 10 Redox-active electrolytes, biredox ionic liquid electrolyte and the related enhanced supercapacitors. (a) A summary of some redox pairs for
electrolyte enhanced supercapacitors. (b) Synthesis of the biredox ionic liquid, where the anions and cations were functionalized with anthraquinone
(AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) moieties, respectively. (c) Capacitances versus full cell or single-electrode voltage. (d) CVs at
5 mV s1 of the PICA electrode at 60 1C with 0.5 M biredox IL in BMImTFSI (solid line), pure BMImTFSI (dashed line), and pure biredox IL (green line).
(e) Self-discharge current test for the devices based on PICA electrodes with BMImTFSI (blue line) or 0.5 M biredox IL in BMImTFSI (red line) at room
temperature (modified from ref. 216, copyright permission from Nature Publishing Group).

enhanced supercapacitors (Fig. 10a), including halides (I/I3
and Br/Br3), vanadium complexes, copper salts, methylene
blue, phenylenediamine, indigo carmine, quinones (Q) and
hydroxyquinone (HQ).
Iodide can produce redox pairs (like I/I3 and I2/IO3)
during the electrochemical process. The ionic sizes of I, I3
(I3 solvated by 4 water molecules), and IO3 (IO3 solvated by
3 water molecules) are 0.39 nm, 0.63 (1.8) nm and 0.57 (1.4) nm,
respectively.181 Owing to these small ionic sizes, these ions can
easily access the micropores and small mesopores of the
porous electrode. For the symmetrically activated carbon super-
capacitors, a nearly two-fold improved specific capacitance and
energy density of 912 F g1 and 19.04 W h kg1 were achieved in
the voltage range of 0.2 to 0.8 V (vs. AgCl/Ag) when 0.08 M KI
was added in a 1 M H2SO4 electrolyte.182 Another supercapa-
citor based on PANi@CNT in a H2SO4/KI (1 M/0.5 M) electrolyte
(x = 3 or 4) since the I ions in a basic electrolyte could be
oxidized into IOx instead of I3.185 The effect of I ion
concentration on the electrochemical performance of a super-
capacitor was studied recently.186 They found that 2 M of alkali
metal iodide solution was an optimal electrolyte for the super-
capacitor based on activated carbon in KOH electrolytes. For too
high concentrations (like 5 M), there might be some problems
with the transport of iodine species due to molecular collisions or
some steric hindrance at the carbon/electrolyte interface and in
the pores of the active material. Interestingly, adding redox
additive I/I3 into a PVA and PEO (poly(ethylene oxide)) polymer
electrolyte system was reported.187,188 Gel polymer electrolytes can
enhance the safety of supercapacitors and solve problems asso-
ciated with electrolyte leakage and corrosion. The Br/Br3 pair

with a higher reduction potential (EBr   ¼ 0:81 V vs. SCE)
3 =Br

displayed a maximum discharge specific capacitance up to
4960 F g1.183 An increase of B105% in the specific energy
density of an asymmetric supercapacitor based on ZrO2@CNT//
WO3@CNT was achieved together with good cycling stability
even after 3000 cycles.184 Besides acid electrolytes, the mixed
KI and basic electrolyte provided the redox couple of IOx/I
compared with iodine (EI3 =I2 ¼ 0:81 V vs. SCE) provided higher
energy density for such kinds of supercapacitors.189,190
The vanadyl sulfate system (VO2+/VO2+) was another
effective addition for redox-active electrolyte enhanced
supercapacitors.191–194 It is well-known that VO2+/VO2+ is one
of the most important ionic species in vanadium redox flow

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batteries. The activated carbon based EDLC in a VOSO4 added
H2SO4 electrolyte showed a maximum specific capacitance of
630.6 F g1 at 1 mA cm2 which is a 43% improvement in the
specific capacitance compared to 1 M H2SO4 (440.6 F g1).192
Compared to V3+/V2+, the VO2+/VO2+ redox reaction has slower
kinetics, thus catalytic processes with hydroxyl or carbonyl
functionalized carbon materials were introduced to enhance
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this redox reaction.194
Fe(CN)64/Fe(CN)63 is a redox pair with very good electro-
chemical reversibility, widely used in electroanalysis and
sensors. There are many reports on Fe(CN)64/Fe(CN)63 as
an additive in the electrolyte for supercapacitors.195–199 For
example, flexible and conductive fabric-supported cauliflower-
like Ni3Se2 exhibited enhanced specific capacitance when intro-
ducing a small quantity of Fe(CN)64/Fe(CN)63 additive into
the aqueous KOH solution.198 The highly soluble and electro-
chemically active hexacyanoferrate ions could easily absorb the
liberated electrons from Ni2+ in Ni3Se2 via the reduction process
of Fe(CN)63 to Fe(CN)64, which would not only promote the
electron gain and loss of Ni ions in the charging/discharging
process but also directly influence the acceleration of the reac-
tion rate for higher capacitance properties.
Using Cu2+/Cu as a redox-active addition in aqueous electro-
lytes, a 10-fold increase in the specific voltammetric capaci-
tance (4700 F g1) was achieved in supercapacitors based
on porous carbon microspheres.200,201 But the cycling stability
was traded-off because of the poor reversibility of the redox
reactions between Cu2+/Cu on the surface of porous carbon
electrodes.201 When Fe2+ ions were added to the H2SO4 and
Cu2+ electrolytes, a stable cyclability was obtained because of
the synergistic effects between Fe3+/Fe2+ and Cu2+/Cu ions,
which might arise from the formation of complexes between
the (FexCuy)2x+ adions and the edge site carbon atoms of the
porous carbon electrodes.
Similarly, the specific capacitance of a fiber supercapacitor
based on RGO was improved more than three times using
sodium molybdate (Na2MoO4) as a redox-active electrolyte.202
The molybdate species (MoO42) can form polymeric ions
(H2MoO4) in acidic medium (PVA/H3PO4 gel electrolyte) with a
+VI oxidation state. H2MoO4 can react with H+ ions via possible
redox couples Mo(VI)/Mo(V) and Mo(VI)/Mo(IV). The S2/Sx2 redox
couple was another effective mediator in alkaline electrolytes.
The specific capacitance of CuS nanotubes was greatly improved
by adding S2/Sx2 into the electrolyte containing 0.5 M NaOH,
0.5 M Na2S and 0.5 M S powder.203 A specific capacitance of
2175 F g1 was obtained even at the current density of 15 A g1.
The S is easily dissolved in concentrated Na2S solution to form
polysulfide anions (Sx2). Then a series of redox reactions will
happen between polysulfide anions Sx2 (x = 2–6) to S2 during
the charging/discharging process.
Organic compounds with functional groups such as hydro-
quinone, quinone and amine were used as intriguing candi-
dates as redox electrolyte mediators for supercapacitors.
Hydroquinone (HQ) is one of the good electrochemically active
organic compounds involved in a two-electron transfer redox
reaction. During the charging process HQ can be oxidized into
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quinone (Q) near the positive electrode. Then during the
discharging process, Q is reduced back to HQ as per eqn (12).
(12)
This redox property of hydroquinone at the electrolyte–
electrode interface contributed to the increase of the total
capacitance for the supercapacitor.204–210 The redox reaction
between p-phenylenediamine/p-phenylenediimine was also
utilized to improve the specific capacitance of a MnO2 based
supercapacitor in KOH electrolyte.211
Apart from hydroquinone, other organic redox mediators (such
as m-phenylenediamine,212 indigo carmine213 and methylene
blue214 and 2-mercaptopyridine215) were reported to improve
the specific capacitance of EDLCs via related redox reactions. For
m-phenylenediamine, the specific capacitance of the super-
capacitor increased not so much (just from 36.43 F g1 to only
78.01 F g1) with the optimal concentration of redox-active
alkaline electrolyte.212 A reversible process associated with the
two-stage redox reaction of indigo carmine (eqn (13)) was found
to be responsible for the capacitance increase.
(13)
The first stage involves the oxidation of the conjugated enol
groups of the leuco-indigo species producing the diketone
structure of the indigo carmine. The second stage involves
the oxidation of indigo through the –NH groups of the indol
structures to yield dehydro-indigo.213 Methylene blue gave rise
to a capacitance enhancement, about 4.5 times higher than that
of the original EDLC based on CNTs, in H2SO4 solution from a
two-electron reversible process (eqn (14)).214
(14)
Unfortunately, these three organic redox mediators led to
limited Faradaic contribution from the redox reactions due to
their large mass. Through the use of a redox-active gel electrolyte
(2-mercaptopyridine–H2SO4–PVA, eqn (15)), a high area specific
capacitance of 507.02 mF cm2 was achieved in wearable fiber-
shaped supercapacitors.215
(15)
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The fiber-shaped supercapacitor derived from an aligned CNT/
mesoporous carbon hybrid fiber was prepared via coating
mesoporous carbon onto aligned CNT sheets, followed by rolling
into a fiber. More detailed discussions will be given on fiber-
shaped supercapacitors in Section 4.4.2.
Self-discharge and leakage currents are the main concerns
when applying redox-active electrolytes in supercapacitors.
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To curb the self-discharge, a bi-redox ionic liquid (IL) was
reported, where the anion and cation were functionalized with
anthraquinone (AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl
(TEMPO) moieties, respectively (Fig. 10b).216 The reversible
electrochemistry of the redox moieties is shown in Fig. 10c.
One couple of peaks at around 0.6 V (vs. AgCl/Ag) was assigned to
the reverse reaction between TEMPO radical (MIMC+–TEMPO )
and TEMPO cation (MIM+–TEMPO+). Two couples of reduction
peaks at around 0.7 and 0.9 V (vs. AgCl/Ag) were consistent
with the reduction of the AQ–PFS moiety to the anthraquinone
radical anion (AQ –PFS) and di-anion (AQ2–PFS). When
using PICA (one type of activated carbon with a significant
amount of pores centred at about 1 nm) as an electrode, the
specific capacitances were 99, 204 and 370 F g1 for 0 and 0.5 M
and pure bi-redox IL, respectively (Fig. 10d). For self-discharge
and leakage current measurements, both supercapacitors based
on PICA with BMIMTFSI and 0.5 M bi-redox IL in BMIMTFSI as
electrolytes presented similar voltage profiles (Fig. 10e). Rapid
voltage decay down to about 2.5 V, followed by a slower decay to
reach a plateau at 1.7–1.8 V, was observed. The calculated
leakage currents were fairly small, only in the range of a few
mA F1. The bulky size of the redox ions impeded diffusion
through the porous electrodes, which greatly reduced the self-
discharge. Moreover, the electrosorption of the multi-charged
ion as well as the higher viscosity of the electrolyte contributed
to the low self-discharge in the bi-redox electrolyte.
4.4 Metal ion hybrid supercapacitors
4.4.1 Li ion capacitors. In 2001, a concept named as a Li
ion capacitor (or Li ion hybrid supercapacitors) was introduced
to improve energy density by integrating the advantages of Li
ion batteries and supercapacitors.217 Its patent was filed by Fuji
Heavy Industry.218–220 Li ion capacitors combine the energy
storage mechanism of supercapacitors and Li ion batteries with
Table 2 The summary of electrochemical performances of the recently reported Li ion capacitor
Li ion capacitor ()//(+) Working voltage (V) Energy density/W h kg1
Li4Ti5O12//C nanosheet 1–3 63
Li4Ti5O12//nanoporous carbon 1–3 57
Mesoporous MnO//activated carbon 0.1–4 227
MnO nanocrystal@C//activated carbon 0.1–4 220
MnNCN//activated carbon 0.1–4 103
Nb2O5@CMK-3//activated carbon 0.5–3 44
NbN//activated carbon 0–4 149
CuBi2O4 microspheres//activated carbon 0.2–3 24
TiO2@RGO//activated carbon 0–3 50
H-TiO2 nanowire arrays//activated carbon 0–3 94
TiO2@EG//EG 0–3 72
Li3VO4@EG//EG 0–3.8 110
a
Cycle number with capacitance retention in brackets.
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anions adsorbing/desorbing onto/from one electrode surface
and Li+ ions intercalating/de-intercalating into/from the bulk of
the other electrode simultaneously. Thus, the overall process
for Li ion capacitors is a cation and anion reversibly consuming
reaction, which is different from that of a ‘‘rocking-chair’’
type reaction as in Li ion batteries. There have been several
excellent reviews on Li ion capacitors reported between 2012
and 2015.20,221–223 For example, various insertion-type electro-
des were systematically summarized for non-aqueous Li
ion capacitors in detail.20 Graphene-based electrode materials
for Li ion capacitors have been highlighted either as positive- or
as negative-electrodes.221 Considering these excellent reviews,
in this section, we will just briefly summarize the latest
advances in Li ion capacitors reported after 2015, as illustrated
in Table 2.
The commonly used supercapacitor-type electrode materials
for Li ion capacitors are carbonaceous materials (activated carbon,
carbon nanotubes, graphene, etc.). Among the carbonaceous
materials, activated carbon is the most widely used due to its
high surface area and relatively low cost. For example, activated
carbon nanosheets were obtained via a bottom-up synthesis
precisely employing sp2 carbon rich 1,2,4,5-benzene tetra-
carboxylic acid (BTCA) as a precursor.224 Its specific surface
area was extended to 2673 m2 g1 by a well-known chemical
activation process using KOH. Nanoporous carbon was derived
from rice husk chemically activated with KOH and H3PO4.225
Rice husk is a naturally abundant biomass waste available
worldwide.
Various battery-type electrode materials are used for Li ion
capacitors, including carbonaceous materials (like graphite and
graphene), metal oxides, intercalation compounds and their
composites. Mesocrystal MnO cubes were synthesized using a
PVA assisted hydrothermal method in one step.226 The micro-
meter-sized mesocrystal MnO cubes consisted of numerous
homoepitaxially aggregated nanocrystals with percolated
porous channels. Spindle-like porous carbon dispersed MnO
nanocrystals were prepared through a hydrothermal method
followed by calcination at different temperatures.227 The calci-
nation temperature of 600 1C was found to be effective for a low
degree of crystallinity, which would benefit the phase transition
in conversion reactions at the negative electrode. Besides MnO,
Power density/kW kg1 Cyclea Ref.
6 6000 (97%) 224
10 2000 (92%) 225
3 5000 (76%) 226
3 3600 (95%) 227
8.5 5000 (99%) 228
8.7 1000 (87%) 229
45 15 000 (95%) 230
2 1500 (85%) 231
4 5000 (77%) 232
15 3000 (78%) 233
3 1000 (68%) 234a
3.87 2400 (86%) 234b
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MnNCN synthesized through a facile solvothermal method
with a following calcination was applied as a new negative
electrode for either Li ion capacitors or Li ion batteries.228 The
Nb2O5/ordered mesoporous carbon (CMK-3) nanocomposite
was synthesized through nanocasting technology using CMK-3
as the hard template and NbCl5 as the precursor.229 CMK-3 is
an ordered mesoporous carbon material with ordered pore
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distribution, large pore volume, high specific surface areas,
and intrinsic high conductivity. The conductive porous nio-
bium nitride (NbN) was prepared by the direct nitridation of
commercial powdery Nb2O5.230 The uniform hierarchical
CuBi2O4 microspheres were synthesized through a facile surfac-
tant-free hydrothermal method.231 The formation of CuBi2O4
microspheres occurs via three different stages: nucleation, Ostwald
ripening, and self-assembly. A TiO2/RGO nanocomposite was
fabricated by microwave-assisted forced hydrolysis.232 TiO2 with
a size of 3 nm is uniformly distributed on the RGO surface.
Prior to construction, the charge-storage performance of a
single electrode in a half cell needs to be evaluated to adjust the
mass loading, because one electrode undergoes a Faradaic
reaction, whereas the other obeys a nonfaradaic mechanism.224
The mass balance between the negative and positive electrodes
is one of the pre-requisites to achieve a superior energy density.
It should be noted that most reports use total mass loading
(negative and positive electrodes) for the calculation of energy
and power densities. For the Li4Ti5O12//rice husk derived carbon,
it showed a pair of redox peaks with considerable area at the
voltage of 2 V.225 The CV curve at 10 mV s1 was wired because
normally the peak separation increased with the scan rate due to
overpotentials caused by the sluggish intercalation/deintercalation
redox reactions. The EIS spectra of MnO//AC displayed a very
low internal resistance of 0.21.226 But this value cannot reflect
the IR drops. The IR drops were obtained from a dynamic state
in the galvanostatic process that could induce the polarization
resistance. While the EIS was measured at the static state of
capacitors and the polarization resistance could be avoided.226
The Li ion capacitor with the spindle MnO as a negative
electrode and activated carbon as a positive electrode offered
a significantly high energy density of 220 W h kg1, comparable
to that of Li ion batteries.227
MnNCN was studied as a negative electrode in Li ion
capacitors with activated carbon as the positive electrode.228
Compared with MnO, the longer bonding length of Mn–N in
MnNCN and the weaker Pauling electronegativity of N lead to a
larger degree of covalent bonding and an increased energy level
related to charge transfer, which will be displayed as a lower
potential plateau. For the negative electrode, the lower
potential benefits the Li ion capacitor with a larger working
voltage, and thus higher energy density. Other Li ion capacitors
composed of Nb2O5/CMK-3 as the negative electrode and
activated carbon as the positive electrode demonstrated an
excellent cycling stability.229 The orthorhombic Nb2O5 has a
2D transport path with pseudocapacitive properties and
only slight structural change during the intercalation process.
Moreover, the CMK-3 could suppress the volume change during
Li+ ion insertion and extraction.
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The fifth family transition metal nitrides present much
better electronic conductivity compared to their oxides and
show potential application as the negative electrode in Li ion
capacitors.230 The Li ion capacitor fabricated by using NbN as
the negative electrode and activated carbon as the positive
electrode exhibited an ultrahigh power density of 45 kW kg1
as well as a superior capacity retention of 95% after 15 000 cycles.
NbN possessed pseudocapacitive charge-storage properties
with fast Li+ ion storage capability. As another novel negative
electrode, CuBi2O4 microspheres were applied in Li ion
capacitors.231 Li+ ions can reversibly intercalate into CuBi2O4,
where the bismuth cations in the CuBi2O4 crystal structure
change their valence state via redox reaction. But Li ion
capacitors based on CuBi2O4 exhibited a low discharge capaci-
tance (26.5 F g1) and low energy density (24 W h kg1) and
further optimization is needed in future work.
TiO2 and its composites were also applied as negative
electrodes for Li ion capacitors.232–234 The main disadvantage
that restricts the applications of TiO2 electrodes is their low
electronic conductivity, which would result in the poor rate
capability of the Li ion capacitor. The common ways to address
this problem are: (1) to tailor the particle size of active materials
to the nanometer-scale,232 (2) hydrogenation treatment,233
and (3) coating a conductive layer.234 For example, Ti3+ was
efficiently introduced into the TiO2 frameworks by a facile
hydrogenation treatment,233 which has also been proved by
our previous work.235 Most of the above Li ion capacitors were
reported based on liquid electrolytes,217–233 easily resulting in
leakage of the electrolytes, which causes serious safety issues.
On the basis of our continuous studies on gel polymer electro-
lyte (GPE) systems,236–239 replacing the liquid electrolyte with a
Li ion conducting gel polymer in Li ion capacitors was achieved
very recently.234 This quasi-solid-state Li ion capacitor achieved
a high energy density of 72 W h kg1. Even discharging within
1 min at a high current density, an energy density as high as
10 W h kg1 was retained. The high ionic conductivity (s) of the
GPE is one of the key points to achieve superior power density
of Li ion capacitors.
4.4.2 Na ion capacitors. Due to the great success of Li ion
capacitors, the development of new power sources combining the
advantages of both supercapacitors and rechargeable batteries
attracts considerable interest. The constraint in the lithium
resources on the earth compels researchers to replace lithium
with other abundant elements in energy storage devices. Sodium,
the second lightest metallic element after lithium, is 4–5 orders
of magnitude more abundant than lithium. In this context, Na
ion capacitors have been explored by integrating the advantages
of Na ion batteries and supercapacitors since 2012.240–242
Similar to Li ion capacitors, the Na ion capacitor couples a
battery-type negative electrode with high capacity and a surface
adsorption based supercapacitor-style positive electrode with
high rate. The negative electrodes for Na ion capacitors include
hard carbon (or biowaste-derived carbon),240,243,244 V2O5,241
Na2Ti3O7,242 Nb2O5,245,246 and NiCo2O4,247 and Na3V2(PO4)3.248
Hydrothermal treatment of different TiO2 precursors with con-
centrated NaOH is a facile and effective way to synthesize
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sodium titanate nanotubes.242 Peanut shell ordered carbon was
prepared by carbonization of peanut shells (1200 1C) in argon,
followed by a mild low temperature (300 1C) activation treat-
ment in air.243 The peanut currently has no commercial end
uses apart from as filler in animal feed or as charcoal. Thus,
peanut shell ordered carbon as the negative electrode for Na
ion capacitors will be truly green because it is derived from
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organic waste products that otherwise possess no economic
value. Nb2O5 nanosheets with exposed (001) facets were pre-
pared by a hydrothermal reaction using niobium foil, hydrogen
fluoride (HF), and lithium hydroxide (LiOH) as the precursors.245
The pH value of the reaction system is very important since it
affects the proceeding of the hydrolysis reaction as shown in
eqn (16) and (17):
4Nb + 20F + 5O2 + 6H2O - 4NbOF52 + 12OH, (16)
2NbOF52 + 3H2O - Nb2O5 + 10F + 6H, (17)
Normally, the [001] direction of Nb2O5 is the preferential
growth orientation due to its lowest energy, leading to 1D
Nb2O5 nanorods.
When the pH value increased to a higher level, the growth
speed for other orientations would exceed the speed of [001].245
NiCo2O4 displays many intriguing advantages of low-cost,
abundant resources and environmentally friendliness. Porous
NiCo2O4 was fabricated via a facile and scalable chemical
deposition route, followed by annealing at 300 1C.247 The porous
NiCo2O4 showed a large specific surface area (190.1 m2 g1) and
high mesopore volume (0.943 cm3 g1). The supercapacitor-type
electrodes for Na ion capacitors are carbon materials, like
activated carbon and graphene. For example, 3D macroporous
graphene was prepared by a microwave-assisted electrochemical
exfoliation in aqueous electrolyte combined with a hard template
method.248 First, the ultrathin graphene nanosheets were
obtained by expansion of graphite in (NH4)2SO4 aqueous
solution under high voltage. Under the high voltage (5–10 V),
SO42 ions together with water molecules intercalated into the
graphitic layers (positive electrode). The gases (SO2 and O2)
produced from SO42 and OH could exert large forces on the
graphite layers, which were sufficient to separate the weakly
bonded graphene layers from one another.249,250 Subsequent
vacuum filtration was then conducted to realize the sandwich-
type assembly of MnCO3 spheres and graphene sheets, followed
by removing the MnCO3 template using HCl. 2D V2C from the
MXene family was also investigated as the positive electrode for
Na ion capacitors.251
V2O5 can accommodate a variety of metal ions, such as Li+
and Na+ ions. However, it generally exhibits poor electronic
conductivity and slow ion diffusion. To solve this problem,
composites of V2O5 nanowires/CNTs were obtained and applied
as the negative electrode for Na ion capacitors.241 The inter-
penetrating porous networks of this composite provided facile
Na+ ion insertion/extraction and fast electron transfer, enabling
the fabrication of high-performance Na ion capacitors in an
organic electrolyte. For sodium titanate, compared with bulk
materials, the predominance of sodium titanate nanotubes
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enabled an excellent rate performance, which could cater to
the demand for supercapacitors.242
The most studied negative electrode for Na ion capacitors
is disordered carbon (or hard carbon) because of its large
interlayer distances (40.38 nm) and disordered structures,
facilitating Na ion insertion and extraction.240,243,244,252 The
assembled Na ion capacitor derived entirely from a single
precursor of biomass waste peanut shells operated within a wide
temperature range (0–65 1C) and achieved an energy density of
above 200 W h kg1 at room temperature.243 Another Na ion
capacitor, in which both the positive and the negative electrodes
were based on peanut skin derived carbon nanosheets, finished
charging/discharging within 20 s with an energy density
of 47 W h kg1.244 The advantages of such kinds of Na ion
capacitors were their simplicity, environmental friendliness
and potential for low cost manufacturing of a device with
identical waste-derived materials as both electrodes.
Nb2O5 with intercalation pseudocapacitance makes it an
ideal negative electrode material in Na ion capacitors.245,246
Nb2O5@C@RGO//AC delivered an exceptionally high energy
density (76 W h kg1) even at a very high power density
(20.8 kW kg1).246 Spinel nickel cobaltite (NiCo2O4) possessed
richer redox chemistry and much higher electronic conductivity
than nickel oxides and cobalt oxides.247 It presented Na ion
insertion/extraction reactions and conversion reactions at
different potentials. Through the effective control of Na ion
insertion/extraction reactions in the NiCo2O4 electrode, the 3 V
class NiCo2O4//activated carbon exhibited a much superior
performance to the theoretical 4.3 V class capacitor. But its
energy density was very low (only 13.8 W h kg1). Hard carbon//
V2CTx showed a maximum voltage of 3.5 V and a relatively high
specific capacitance.251 But cyclability was not satisfactory and the
capacity retention was 70% after only 300 cycles. The potential of
the V2CTx electrode went slightly beyond the optimum operating
potential range of 1 to 3.5 V, which led to irreversible redox
reactions. Interestingly, two Na ions can be extracted from or one
Na ion can be inserted into the Na3V2(PO4)3 host, exhibiting two
distinctive plateaus of 3.4 and 1.6 V (vs. Na+/Na) with a theoretical
capacity of 118 and 59 mA h g1, respectively.252 So Na3V2(PO4)3
can be applied as either a positive electrode or negative electrode
in Na ion capacitors.253
Recently, our group successfully demonstrated the first
quasi-solid-state Na ion capacitor in a Na+ ion conducting gel
polymer electrolyte with nanoporous carbon nanoparticles and
macroporous graphene as the negative and positive electrodes,
respectively.248 A Na+ ion conducting gel polymer using a
P(VDF–HFP) membrane as the matrix was utilized as the
electrolyte. The color of the membrane changed from white to
transparent, indicating that the organic electrolyte was success-
fully entrapped in the pores of the P(VDF–HFP) matrix (Fig. 11a).
This quasi-solid-state Na ion capacitor operated at a high voltage
up to 4.2 V (Fig. 11b) with an energy density of 168 W h kg1.
In the case of this quasi-solid-state device, the lamination
(electrodes and polymer electrolyte), stacking, and hermetic
sealing processes are much simpler and cost-effective. Moreover,
polymers are lightweight, flame-resistant, and can be shaped to
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Fig. 11 The quasi-solid-state electrolyte, electrochemical behavior
and flexible device for Na ion capacitors. An optical photograph showing
the polymer electrolyte (a) before and (b) after the gel for the quasi-
solid-state sodium ion capacitor (hard carbon//graphene). (c) Its galvano-
static charge/discharge curves from 0 to 4.2 V at different current
densities (modified from ref. 248, copyright permission from Wiley).
(d) Schematic illustration of the flexible Na ion capacitor. (e) The capaci-
tance retention of the flexible Na ion capacitor under different bending
conditions (modified from ref. 254, copyright permission from the
American Chemical Society).
satisfy the requirements for reliable applications. Regrettably,
the power density of such Na ion capacitors is relatively not
high. Using the same gel polymer electrolyte, another quasi-
solid-state Na ion capacitor was designed based on urchin-like
Na2Ti3O7 as the negative electrode and peanut shell derived
carbon as the positive electrode (Fig. 11c).254 Such a flexible quasi-
solid-state Na ion capacitor was sealed by two thin pieces of foil/
poly bag film. It achieved an energy density of 33.2 W h kg1 even
at a high power density of 11.2 kW kg1. Importantly, it presented
remarkable mechanical robustness and there was no obvious
capacitance loss under different bending conditions (Fig. 11d).
Such superior performances indicate that the quasi-solid-state Na
ion capacitor may be the key to bridge the gap between recharge-
able batteries and supercapacitors, meanwhile meeting the safety
demands of electronic devices.
4.4.3 Other metal ion capacitors. Apart from Na ion based
systems, K ion based energy storage systems also offer an
attractive alternative due to the low cost and natural abundance
of K resources. K metal has a lower redox potential (2.93 V for
K+/K vs. SHE compared to Na with 2.71 V for Na+/Na vs.
SHE).255 Although the atomic weight ratio of K against Li is
5.7 (=39/6.9), the ratio of (P2-type K2/3CoO2)/(LiCoO2) is only
1.19, which means that the atomic weight of K does not
remarkably affect the gravimetric capacity and total weight of
the K ion-based energy storage system. Like Li ion capacitors or
Na ion capacitors, exploiting electrode materials holds the key
for developing high-performance K ion capacitors. Recently, a
graphite–polyacrylate electrode was proposed as a negative
electrode for 4 V class K ion capacitors.256 Sodium polyacrylate
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was utilized as the binder to improve the solid electrolyte
interphase (SEI)-passivation. KClO4 and KBF4 were almost
insoluble in propylene carbonate (PC) while KPF6 was not
completely dissolved into ethylene carbonate/diethyl carbonate
(EC/DEC). The electrolyte used in the K ion capacitors was 1 M
KFSI dissolved into EC/DEC. The authors also showed that the
ionic conductivities at ambient temperature were 9.3, 9.7 and
10.7 mS cm1 for 1 M LiFSI, NaFSI, and KFSI in EC/DEC,
respectively.256 The high conductivity is very important for ion
transfer in electrolytes and at the electrode/electrolyte interface,
especially in the application of supercapacitors. K+ ions can be
intercalated into graphite to form KC8 with a stage-1 structure
with a capacity of 279 mA h g1. However, at a low potential
(close to 0–0.2 V vs. K+/K), both K metal plating and inter-
calation of K ions into the graphite would occur on the negative
electrode. In such a case, the emerging major problem is the
growth of K-dendrites at such low potential, causing safety
hazards and exposing the device to wide safety concerns. It
should be noted that K metal is violently reactive compared to
Li and Na metals and its melting point (64 1C) is much lower than
others. In this regard, a safe aqueous K ion capacitor was built
based on KxMnO2 as an active material in a K2SO4 electrolyte.145c
It worked in the entire voltage region of 0 to 1.9 V with no more
than 2% capacitance loss after 10 000 cycles. Another hybrid K ion
capacitor (KIC) was assembled based on activated carbon and
high quality cubic Prussian blue in a K2SO4 electrolyte solution.257
It presented a maximum energy density of 28 W h kg1 with
capacity retention of nearly 98% over 1200 cycles. Prussian blue
and its analogues (PBAs), one class of MOFs, have received
attention from the community owing to their impressive electro-
chemical performance with reversible intercalation of different
metal ions as well as easy synthesis procedures.1c
Beyond monovalent metal ion systems, multivalent metal-
ion (Al3+ etc.) based energy storage systems are of interest due
to their potentially higher energy. Aluminum (Al) is the most
abundant metal element in the Earth’s crust.258 Moreover,
the aluminum-based redox couple engages a three-electron
transportation during the electrochemical charge/discharge
reactions, which offers viable storage capacity relative to the
Li- or Na-ion capacitors from a single electron. Reversible Al ion
storage behaviors in Prussian blue analogues and MoO3 nano-
tubes were recently proposed for aqueous Al ion capacitors.259,260
The Al ion capacitor, using Al0.2CuFe–PBA as the positive
electrode and activated carbon as the negative electrode,
achieved an energy density of 13 W h kg1. At a current rate
as high as 100C (34 mA cm2), its capacitance remained more
than 65% of that for discharging at 1C.259 Another Al ion
capacitor, assembled by using a composite of MoO3 nanotubes
coated by a conductive polypyrrole (PPy@MoO3) as the negative
electrode and activated carbon as the positive electrode, pre-
sented an energy density of 30 W h kg1 with an operation
voltage up to 1.5 V in aqueous electrolyte.260 Its cycling stability
with 93% retention of the initial specific capacitance after 1800
cycles was competitive to those of the latest reported Li/Na ion
capacitors as discussed in the above section. The shell PPy
can absorb the small amount of acid from the hydrolysis of
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0.5 M Al2(SO4) electrolyte capacitors, which alleviates the acid
etching of the core MoO3. No new phases emerge from the
ex situ XRD spectra when the Al3+ ions intercalate into MoO3.
Yet, CV scans of MoO3 in aqueous Al2(SO4)3 electrolyte do not
support a strictly capacitive process. The b value is close to 0.5,
indicating that the kinetics may be solid-state diffusion. Thus,
whether the observed Al ion intercalation in MoO3 can be
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4.5 Microsupercapacitors
4.5.1 Fiber-shaped microsupercapacitors. Recently, fiber-
shaped microsupercapacitors have been demonstrated with a
twisted fiber configuration made from ZnO nanowire electrodes,
which utilize 1D cylindrically shaped fibers as electrodes.261,262
Currently, there are mainly three types of device configurations
for fiber-shaped microsupercapacitors, including two parallel

categorized as a pseudocapacitive response is not clear. Another
pending question is whether there is a dehydration reaction
process during trivalent Al3+ ion insertion. Al3+ ions have
a smaller Shannon radius (39 pm) compared to Na+ ions
(102 pm), K+ ions (151 pm) and Mg2+ ions (72 pm). But, Al3+
ions, with a radius of 480 pm, have very strong ion–water
interactions due to their high charge. Of course, further direct
evidence about the reaction mechanism based on some in situ
characterization techniques is further needed.
Fig. 12 Schematic illustration of fiber-shaped microsupercapacitors with
different configurations. (a) Parallel electrodes, (b) twisted electrodes and
(c) coaxial electrodes.
fibers (Fig. 12a), two twisted fibers (Fig. 12b) and one coaxial
fiber (Fig. 12c). Parallel fiber microsupercapacitors were
produced by integrating more fiber electrodes on the planar
substrate, while the twisted-fiber microsupercapacitors were
fabricated by twisting two fiber electrodes together with a solid
state electrolyte between them.262 The third one, a coaxial-fiber
microsupercapacitor, was achieved by layer-by-layer assembly of
a core fiber electrode, a solid state electrolyte, and an outer
electrode layer.263,264 Currently, several types of carbonaceous
fibers and carbon-based composite fibers containing pseudo-
capacitive materials are applied for fiber-shaped microsuper-
capacitors, as summarized in Table 3. In some cases, only
partial data were listed because some information was missing
in the original references.
A simple dip-coating method was applied to form pen-ink-
coated metal wires, which were then assembled into parallel fiber-
shaped microsupercapacitors.265 A spacer wire was utilized for
the efficient separation of the two fiber electrodes. It displayed
a maximum capacitance of 19.5 mF cm2, an energy density of

Table 3 The summary of electrochemical performances of recently reported fiber-shaped microsupercapacitors

Working
Fiber-shaped microsupercapacitor ()//(+) Configuration voltage (V) Energy density Power density Cyclea Ref.
6 2 2
Pen ink//pen ink Parallel 0–1 2.70  10 W h cm 9.07 mW cm 15 000 265
Ink-gel activated carbon//ink-gel Coaxial 0–0.8 — — — 266
Activated carbon@cotton//activated carbon@cotton Parallel 0–0.8 — — 3000 (77%) 267
Porous C//porous C Parallel 0–0.8 3.7  107 W h cm1 70.3 mW cm1 4000 (88%) 268
CFs//CFs Twisted 0–1 0.35 mW h cm3 3 W cm3 10 000 (91%) 269
Activated carbon@CF//activated carbon@CF Twisted 0–1 6.5 mW h cm1 220 mW h cm1 10 000 (87%) 270
CNT//CNT Coaxial 0–1 1.88 W h kg1 755.9 W kg1 11 000 (100%) 271
Graphene//graphene Parallel 0–1 — — 2000 (94%) 272
Graphene//graphene Coaxial 0–0.8 17.5 mW h cm2 819 mW cm2 10 000 273
Graphene@CNT//graphene@CNT Parallel 0–0.8 — — 5000 274
Graphene@CNT//graphene@CNT Twisted 0–1 2.4 mW h cm3 0.016 W cm3 10 000 275
N-Doped graphene@CNT//N-doped graphene@CNT Parallel 0–1 6.3 mW h cm3 1085 mW cm3 10 000 (93%) 276
Graphene@CNT//graphene@CNT Parallel 0–1 2.8 mW h cm1 379 mW cm1 10 000 (92%) 277
Graphene@CNT//graphene@CNT Parallel 0–0.8 — — 1000 (80%) 278
Activated carbon@graphene//activated Twisted 0–0.8 2.5 mW h cm3 5 mW cm3 10 000 (94%) 279
carbon@graphene
MnO2@CNT//MnO2@CNT Twisted 0–2 92.84 mW h cm3 3.87 W cm3 1000 280
MoS2@CNT//MoS2@CNT Twisted 0–0.8 0.55 W cm3 3 mW h cm3 10 000 (92%) 281
NiCo2O4@PPy@CNT//NiCo2O4@PPy@CNT Parallel 0–1 17.5 W h kg1 4 kW kg1 10 000 (87%) 282
MnO2@graphene//MnO2@graphene Twisted 0–0.8 – — 1000 (80%) 283
PEDOT–PSS@graphene//PEDOT–PSS@graphene Parallel 0–0.8 27.1 mW h cm2 200 mW cm2 10 000 (96%) 284
N-Doped graphene@CNT//MnO2@graphene@CNT Parallel 0–1.8 5 mW h cm3 929 mW cm3 10 000 (87%) 285
V2O5@PANI@CFs//MnO2@PPy@C Coaxial 0–2 10.8 mW h cm2 30 mW cm2 5000 286
OMC@CNT//MnO2@PEDOT–PSS@CNT Twisted 0–1.8 11.3 mW h cm3 2.1 W cm3 10 000 (85%) 287
CNT//MnO2@ZnO2@CNTs Twisted 0–1.8 13.25 mW h cm2 2.1 W cm2 1000 (97%) 288
Porous C@CF//NiCo2O4@CF Twisted 0–1.65 0.53 mW h cm3 1 W cm2 3000 (92%) 289
CoFe2O4@PANI@graphene//Co(OH)2 Parallel 0–1.5 27 mW h cm3 625 mW cm1 1000 290
MoS2@graphene@CNTs//graphene@CNT Parallel 0–1.6 — — 7000 291
Ni3S2 nanorod array//pen ink Coaxial 0–1.4 0.81 mW h cm3 285 mW cm3 3000 (93%) 292
OMC//Ni(OH)2 Twisted 0–1.5 2.16 mW h cm3 1.6 W cm3 10 000 (70%) 293
a
Cycle number with capacitance retention in brackets.

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2.70  106 W h cm2, and a power density of 9.07 mW cm2.
Pen ink possesses advantages of low cost, high stability, and
well-established industrial production. A coaxial fiber-shaped
microsupercapacitor was demonstrated using ink-gel activated
carbons.266 It consisted of three active coating layers and one
silver paint layer for the current collector. The first and
third active layers served as positive and negative electrodes,
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respectively, prepared by using Chinese ink and activated
carbon slurry. The second layer was an electrolyte using a
PVA–H3PO4–H2O gel solution. Its capacitance was calculated
to be 0.1 mF cm1 (3.18 mF cm2). Activated carbon can also be
introduced into swelled cellulose yarns (cotton, linen, bamboo,
and viscose) through a welding process.267 The natural fiber
welded material yielded high activated carbon mass loadings per
length of yarn ranging from 0.35 mg cm1 up to 0.62 mg cm1,
achieving high capacitance per length of 8 mF cm1 up to
37 mF cm1 at 2 mV s1, respectively. However, not all of the
electrode yarns are suitable for knitting. Only the activated
carbons, linen, bamboo and viscose yarns, were successfully
knitted into symmetric fabric devices. Another fiber-shaped
microsupercapacitor was fabricated by using porous carbon
derived from the dead leaves of Ficus religiosa.268 Its calculated
length capacitance and energy density were 4.2 mF cm1 and
37.3  108 W h cm1, respectively.
Carbon fiber (CF) consists of graphite filaments of
about 5–10 mm in diameter. Pristine CF has a low surface area
(o10 m2 g1) and poor porosity. Activated CF was utilized to
construct fiber-shaped microsupercapacitors with excellent
flexibility and weavability.269
Activation of pristine CFs was achieved by oxidative exfolia-
tion with KMnO4/H2SO4, annealing in air, and reducing with
a mixture of hydrogen iodide (HI) and acetic acid (AcOH).
The specific volumetric capacitance of the activated CF tows
presented a 22-fold increase up to 14.2 F cm3. Their capaci-
tance retention was maintained at nearly 100% when bending
from 01 to 1801. Conductive CFs can act as current collectors
in fiber-shaped microsupercapacitors and as substrates for
depositing large surface area activated carbon particles.270
A 10 cm long fiber-shaped microsupercapacitor, with the com-
position of 2.2 mg cm1 of activated carbons and 1 mg cm1 of
CF, exhibited an ultra-high length capacitance of 45.2 mF cm1
together with an energy density of 6.5 mW h cm1. It retained an
energy density of 3.0 mW h cm1 even at a higher power density
of 220 mW h cm1.
Due to their remarkable mechanical, electrical, and
thermal properties, carbon nanotubes (CNTs) were widely
studied as electrode materials for fabricating fiber-shaped
microsupercapacitors.271 CNT fibers were dry-spun from CNT
arrays. The resulting fiber showed electronic conductivity at the
level of 102–103 S cm1. The microsupercapacitor based on
CNT fibers in a coaxial structure displayed a maximum dis-
charge capacitance of 59 F g1 (32.09 F cm3 or 29 mF cm1 or
8.66 mF cm2). This value is much higher than that of micro-
supercapacitors by twisting the same CNT fibers together,
suggesting that the coaxial structure allows an adequate trans-
portation of ions between the two electrodes.
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Graphene nanosheets and its composites were also
made into continuous fibers as electrodes for fiber-shaped
microsupercapacitors.272–279 For example, a graphene-based
coaxial fiber-shaped microsupercapacitor was fabricated with
a continuous liquid crystal wet-spun core fiber and a dip-coated
cylinder sheath fiber as two electrodes.273 The face-to-face
structure of the two electrodes showed lower solution resis-
tance compared with the twisted-structured graphene based
microsupercapacitor. Graphene nanosheets were incorporated
among neighboring CNTs, serving as effective bridges to improve
the charge transport because of strong p–p interactions
between CNTs and graphene.274
As expected, the specific capacitance of fiber-shaped micro-
supercapacitors was improved by incorporating second phases
such as conducting polymers or metal oxide into carbon
materials. Pseudocapacitive electrode materials have higher
specific capacitance but poor conductivity. The incorporation
of MnO2 nanoparticles,280 MoS2 nanosheets281 and NiCo2O4
nanowires282 into CNT fibers has been achieved as electrodes in
recent years. After the deposition of second phases, the high
flexibility, strengths and conductivities in the CNTs were all
well maintained. Compared with the CNT fiber, the graphene
fiber demonstrated much higher loading capability and better
flexibility for a second phase.283,284 The electronic conductivities
of the hollow graphene/conducting polymer composite fibers
reached 4700 S m1, in which the conducting polymer was a
composite of poly(3,4-ethylenedioxythiophene) with poly(styrene-
sulfonate) (PEDOT:PSS).284 The obtained fiber-shaped micro-
supercapacitor demonstrated a specific areal capacitance up to
304.5 mF cm2 (or 143.3 F cm3 or 63.1 F g1) at 0.08 mA cm2.
All the above reported fiber-shaped microsupercapacitors
were based on a symmetric device configuration with two
identical fiber electrodes, and their operating voltages were
limited to 0.8–1 V.265–284 Apart from increasing the specific
capacitances of the electrode materials, extending the voltage
window makes an enormous contribution to the increase of
energy density as well. A promising strategy to achieve both
wide voltage window and high energy density is to construct
asymmetric fiber microsupercapacitors. Asymmetric super-
capacitors can make full use of two different electrodes, exhi-
biting two different potential windows in the same electrolyte.
Accordingly, the working voltage windows increase and thus
the energy densities are improved significantly. MnO2 and its
composites are the most commonly used positive electrode
materials for asymmetric fiber-shaped microsupercapacitors
with carbon or other metal oxides as negative electrodes.285–288
Mixed transition–metal oxides (like NiCo2O4 and CoFe2O4) were
also promising positive electrodes for asymmetric fiber micro-
supercapacitors due to their good electrochemical properties,
such as excellent reversibility and conductivity.289,290 Besides
metal oxides, MoS2, Ni3S2 and Ni(OH)2 were also reported as
positive electrodes for asymmetric fiber microsupercapacitors
recently.291–293 MoS2 nanosheets can efficiently store charges by
pseudocapacitance within a positive potential window resulting
from the Faradaic charge-transfer process on the Mo center
or the formation of a double-layer at the electrode/electrolyte
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interface because of the adsorption of protons or other cations
on the nanosheet. These asymmetric fiber-shaped microsuper-
capacitors operated in a wide potential window up to 1.4 V even
to 2.0 V,285–292 which greatly enhanced the energy densities of
fiber-shaped microsupercapacitors.
4.5.2 Plane microsupercapacitors. The initial generation of
2D micro-supercapacitors is based on a planar architecture like
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For the first method, normally, there were two different steps
after fabricating interdigital current collectors: removing the extra
active materials without coating the current collector296–302 or
depositing active materials on the current collector.303–308 Taking
one example in Fig. 13a for illustration, a thin film of graphene
was obtained on a modified silicon wafer by rapidly reducing
a GO film from spin-coating a GO dispersion. Next, micro-

thin film batteries. These types of devices usually consist of
thin film electrodes with a thickness of micro-size. Currently,
such kinds of thin film devices are commercially available and
are not included here. In this section, we focus on the plane
micro-supercapacitor with interdigital electrode architecture
(fingers). As early as 2003, interdigitated micro-supercapacitors
were achieved through the electrodeposition of conducting
polymers on interdigital gold or platinum micro-electrodes on
Si/SiO2 substrates.294 These gold or platinum microelectrode arrays
were prepared by UV photolithography and a wet etching method.
Actually, the key step for micro-supercapacitors with in-plane
interdigital electrode architecture was the advanced microfabrica-
tion method, which could accurately control very small distances
between the interdigital electrodes.295 Currently, many methods are
reported for such micro-supercapacitors, such as (1) the mask-
assisted current collector protection method, (2) laser-patterning
directly performed on a thin film of active material to form the
interdigital electrodes, (3) printing and (4) spray coating.
mask techniques were applied to manufacture interdigital
microelectrode patterns through the deposition of gold current
collectors. After that, oxidative etching in oxygen plasma was
utilized to remove the extra graphene film without the current
collector. Finally, a GPE (H2SO4/PVA) was drop-casted onto the
interdigital electrodes and solidified.297 Such microdevices
operated at an ultrahigh rate of up to 1000 V s1, which was
several orders of magnitude higher than that of conventional
supercapacitors. If there are any metal oxides in the electrodes,
the device needs to be placed in an acid solution to remove the
residual metal oxides.300 Another microsupercapacitor based
on micrometer-thick PANi@graphene was developed using the
same method.301 It delivered an ultrahigh areal capacitance
of 368 mF cm2 and a landmark volumetric capacitance of
736 F cm3, which were very high values among the reported
state-of-the-art plane microsupercapacitors.301 Deposited active
materials on the interdigital current collector were also applied
to obtain plane microsupercapacitors. Onion-like carbon (OLC)

Fig. 13 Some fabrication methods reported for plane micro-supercapacitors. (a) Schematic illustration of the fabrication of RGO based microsuper-
capacitors via the mask-assisted current collector protection method (modified from ref. 297, copyright permission from Nature Publishing Group).
(b) Schematic of the carbon anion based micro-supercapacitors. (c) Optical image of its interdigital fingers with 100 mm spacing. (d) Scanning electron
microscope image of the cross-section of the carbon anion electrode. (e) Plot of specific capacitance versus scan rate (modified from ref. 303, copyright
permission from Nature Publishing Group). (f) Schematic illustration of the fabrication of RGO based micro-supercapacitors via the laser-patterning
direct writing method. (g) An optical photograph showing a lot of RGO based microsupercapacitors on a DVD media disc (modified from ref. 311,
copyright permission from Nature Publishing Group).

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particles, produced by annealing nanodiamond powder at
1800 1C, were deposited from colloidal suspensions using an
electrophoretic deposition technique (EPD) onto interdigital
gold current collectors patterned on silicon wafers (Fig. 13b).
It showed regular widths of 150 mm and an interspace of 50 mm
between neighbouring electrode fingers (Fig. 13c). The micro-
device was constructed with 16 interdigital electrodes with
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thicknesses of 7 mm (Fig. 13d). The OLC-based micro-super-
capacitors showed a specific capacitance of 0.9 mF cm2
even at 100 V s1 (Fig. 13e). It also sustained very high scan
rates, like electrolytic capacitors. In contrast, the capacitance
of microdevices based on 5.0 mm-thick activated carbon
(1700–1800 m2 g1) fell quickly at a higher scan rate.303
Many graphene based microsupercapacitors were fabricated
using an unconventional method of direct laser reduction and
patterning of hydrated GO.309–313 The laser patterned part of
the GO film (reduced GO) worked as the electrodes. When GO
absorbed high-intensity light, it was converted into graphene.
While the hydrated GO between the electrodes served as the
separator since hydrated GO was simultaneously a good ionic
conductor and an electrical insulator.309 Compared with the
above methods utilizing interdigital current collectors, this direct
laser patterned technique does not require masks, expensive
materials, post-processing or clean room operations. Later, more
than 100 microsupercapacitors were produced on a single disc in
less than 30 minutes by direct laser writing on GO films using a
standard LightScribe DVD burner (Fig. 13f and g).311 Using
LightScribe, interdigitated electrodes were precisely patterned
with a lateral spatial resolution of 20 mm. The production of 3D
porous graphene films from polyimide was achieved by a CO2
infrared laser.314,315 The sp3-carbon atoms were photothermally
converted to sp2-carbon atoms by pulsed laser irradiation. The
ultra-polycrystalline nature of this laser induced graphene had an
abundance of grain boundaries (GBs), which were composed of
pentagon and heptagon pairs. These defects were more ‘metallic’
than regular hexagons and could enhance the charge storage
performance from theoretical calculations.314
Interdigitated electrodes were also obtained by cutting the
active material films.316,317 However, this cutting method by hand
is not suitable for large-scale production of microsupercapacitors.
Very recently, the direct printing of microsupercapacitors was
developed by spray-coating an electrochemically exfoliated gra-
phene hybrid ink through a shadow mask with the designed
geometry.318 The thickness of the patterned microelectrodes was
easily controlled by adjusting the amount of graphene ink and
the number of spray-coating cycles. To meet the industrial
requirements for scale-up production of microsupercapacitor
arrays, an inkjet printing technique was realized using a com-
mercial inkjet printer.318 Such printable microsupercapacitors
showed great potential for ‘‘ultra flexible’’ device architectures,
which could be attached to a human finger or other body parts.
Besides graphene ink, CNT ink was also carefully micropipetted
into two micro-channels perpendicular to the finger-like micro-
channels through a wetting-induced micro-patterning fabrication
approach.319 The flow of the CNT ink was guided and patterned
by hydrophilic open micro-channels on PDMS.
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Asymmetric micro-supercapacitors were developed to extend
their operating voltage windows.320,321 For example, MnO2
nanoflowers were selectively electrodeposited on one set of
graphene microelectrodes produced by direct writing on GO
films using a consumer-grade LightScribe DVD burner.321
Charge balance between the two electrodes was achieved by
controlling the deposition time of MnO2 at the positive elec-
trode and the thickness of the graphene film at the negative
electrode. In addition, the micro Li ion capacitor was fabricated
by using a special micro electro-mechanical systems fabrication
technology.320 This micro Li ion capacitor worked at a voltage
range of 0–3.8 V. Compared with the symmetric AC super-
capacitor in a LiPF6 electrolyte, it achieved much higher energy
density due to both higher capacitance and extended voltage.
4.5.3 3D microsupercapacitors. The tailored dimensionality
is a new development direction in the field of microsuper-
capacitors. Microsupercapacitors could gain enormous benefits
through a redesign from 2D to 3D. For example, higher areal
energy density could be easily obtained without loss in power
density, simply by increasing the height of an interdigitated
electrode.322 Moreover, the 3D microarchitecture can bring
increased energy density by fully utilizing the limited volume
available.
Several 3D microsupercapacitors have been reported so
far based on Pt@RuO2 core–shell nanotubular electrodes,323
ripple-like CNT@RuO2,324 and RuO2 nanotubes.325 Because of
facilitated transport of protons and electrons, high specific
capacitances (100–320 mF cm2) were obtained, demonstrating
high utilization of RuO2 electrodes. The application of nano-
structured MnO2 materials on 3D Si nanowires arrays326–328 and
Ni nanocone arrays329 also emerged as a promising strategy for
preparing high-performance 3D microsupercapacitors. MnO2
was normally electrodeposited on the resulting 3D conducting
architecture. Its thicknesses could be controlled according to the
number of deposition pulses.
The above 3D designs were mainly focused on the electrodes,
while architectures of devices may be more essential in designing
3D microsupercapacitors. Among the 3D concepts that have
emerged for microsupercapacitors, three types of device archi-
tectures were suggested, which were similar to those 3D micro-Li
ion batteries, as shown in Fig. 14. The first one is based on
interdigitated rod electrodes (Fig. 14a). The positive and negative
electrodes with 1D nanorods alternate to form ordered 3D arrays
Fig. 14 Schematic illustration of 3D microsupercapacitors with different
configurations. (a) Interdigitated rod electrode, (b) interdigitated plate
electrode, and (c) concentric electrode.
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separated by the electrolyte. The second is constituted by
interdigitated plates rather than rods (Fig. 14b). Alternative
layer stacked Au/MnO2/Au electrodes for such microsuper-
capacitors were fabricated through combining laser printing
technology with the electrodeposition technique.330 Besides,
the 3D printing technique can be applied to build up such
microstructures, which has been demonstrated in Li ion
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batteries.331,332 The third one is a concentric 3D architecture
(Fig. 14c), in which a rod-shaped electrode is coated by an
electrolyte layer and the remaining volume is filled by the other
electrode. Thus, the volume is fully utilized and the energy
density can be increased. However, such microarchitecture is just
conceptual and far from reality. Generally, the manufacturing of
3D microsupercapacitors involves tedious processes, and cost-
saving production technologies are highly desirable in this field
in the future.
4.6 Multifunctional supercapacitors
4.6.1 Electrochromic supercapacitors. Some electrode
materials reversibly change their colors during electrochemical
reduction/oxidation processes, which can be clearly observed
when they are fabricated on transparent current collectors. This
phenomenon is known as electrochromism.333 Electrochromism
shows great potential application in variable transmittance
windows such as in energy-efficient architecture, non-emissive
information displays, and variable-reflectance mirrors.334
Electrochromic materials, discovered in the late 1960s, include
various transition metal oxides and conducting polymers.335 If
a supercapacitor can change its color according to its charge/
discharge state, its charge/discharge states can be monitored by
simple visual inspection.
The important parameters of electrochromism are coloration
efficiency (CE) and the switching time. The coloration efficiency
(CE) is defined as the change in optical density (DOD) per unit
charge (DQ) into the electrode. It can be calculated from the
following formula:
CE(l) = DOD(l)/DQ = log(Tb/Tc)/DQ, (18)
where Tb and Tc denote the transmittance in the bleached and
colored states, respectively, at a certain wavelength. The switching
time is defined as the time required for a system to reach 90%
of its full optical modulation, which is also a direct indicator of
the kinetics in the electrochemical process.336
The most commonly used electrochromic oxides for super-
capacitors are based on tungsten oxides.337–340 Following eqn (19),
[WO3]bleached + xH+ + xe 2 [HxWO3]colored (19)
the color of the WO3 electrode changes from transparent to
dark blue due to the increasing formation of blue color center
W5+ polarons during the discharge process. While the W5+ was
oxidized back to the higher valence states during the charge
process, accompanied by a color loss due to the extraction of
H+ ions from the WO3 film. WO3 films deposited on fluorine-
doped tin oxide (FTO) glass exhibited a high specific capaci-
tance of 639.8 F g1, with an abrupt decrease in optical
transmittance from 91.3% to 15.1% at a wavelength of
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633 nm when a voltage of 0.6 V (vs. Ag/AgCl) was applied.337
Actually, the capacitance of WO3 film was thickness-dependent.
The total electrochemically stored charge in WO3 contained
three parts: the Faradaic contribution from the slow H+ ion
insertion process (solid-state ion diffusion), the Faradaic con-
tribution from the fast charge-transfer process at the surface
(pseudocapacitance), and the nonfaradaic contribution from
the fast electric double layer effect.338 The 100 nm-thick WO3
film exhibited the highest charge capacity at high rates, and
more than 78% stored charges were attributed to capacitive
effects at a scan rate of 5 mV s1.338 Besides the active
materials, another key component of electrochromic super-
capacitors is the current collector, which not only needs to be
highly transparent but also highly conductive. The most commonly
used transparent conducting current collectors are indium tin
oxide (ITO)-coated glass and FTO-coated glass.337,338 However,
ITO and FTO as transparent current collectors are unsuitable
for flexible electronics applications due to their brittleness and
the high cost of the preparation procedure. Thus, silver grid/
polyethylene terephthalate (PET) transparent electrodes coated
with one layer of PEDOT:PSS were introduced to WO3-based
electrochromic supercapacitors.339 The WO3 on the silver grid/
PEDOT:PSS hybrid film displayed specific capacitances of 221.1,
195.4, 168.6, 153.1, and 148.6 F g1 at 1, 2, 5, 8, and 10 A g1,
respectively. Furthermore, the WO3 on the silver grid/PEDOT:PSS
hybrid film showed an effective color change during fast charge
and discharge processes with a high coloration efficiency (CE)
of 124.5 cm2 C1.
Another electrochromic oxide for supercapacitors is nickel
oxide (NiO) and the schematic reaction is summarized in eqn (20).
[NiO]bleached + OH  e 2 [NiOOH]colored. (20)
The color of the NiO electrode changes from brown (colored
state) to transparent (bleached state). Electrochromic super-
capacitors based on direct growth of NiO nanoparticle films on
ITO glass achieved short switching time for coloration and
bleaching (only 11.5 and 9.5 s).341
It had an outstanding stable and reversible electrochromic
effect, which sustained a transmittance modulation of about
90.8% of the initial value after 1000 cycles. Supercapacitors
built from NiO nanoflake films displayed a high areal capaci-
tance of 74.8 mF cm2 with a large transmittance modulation of
40% and a CE of 63.2 cm2 C1 at a wavelength of 632.8 nm.342
Besides NiO, supercapacitors made from gyroid-structured
V2O5 electrodes exhibited a specific capacitance of 155 F g1
in lithium salt electrolytes with a strong electrochromic color
change from green/gray to yellow during the charge/discharge
process.343
Apart from metal oxides, PANi films have been widely explored
in applications of electrochromic supercapacitors.344–346
PANi films exhibit reversible color changes from transparent
leucoemeraldine to yellow-green emeraldine then to dark blue-
black pernigraniline. As a good illustration, asymmetric super-
capacitors were fabricated from two electrochromic materials
with W18O49 as the negative electrode and PANi as the positive
electrode.346 Both electrode materials in this asymmetric
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Fig. 15 (a) Galvanostatic charge/discharge curves of W18O49 nanowires and PANi at different current densities. In situ optical response of W18O49
nanowires and PANi at 633 nm showing transmittance variation with (b) potential and (c) time (modified from ref. 346, copyright permission from the
American Chemical Society).
supercapacitor possessed excellent electrochemical and elec-
trochromic behaviors, which operated in different potential
windows, 0.5 to 0 V (W18O49) and 0–0.8 V (vs. Ag/AgCl)
(PANi) as shown in Fig. 15a. The change in coloration of the
PANi during oxidation commenced at a potential of 0.2 V (vs.
Ag/AgCl) and ended at 0.8 V (vs. Ag/AgCl), while the response for
the W18O49 started at 0.2 V (vs. Ag/AgCl) and finished at 0.6 V
(vs. Ag/AgCl) during reduction (Fig. 15b). One electrode was
colored while the other was bleached. In addition, this electro-
chromic supercapacitor displayed excellent cycling properties
with no signs of degradation through repeated cycles (Fig. 15c).
Integrating electrochromism into a supercapacitor presents a
significant opportunity in the development of future super-
capacitors with imaginative and humanization features.
4.6.2 Self-healing supercapacitors. To restore the super-
capacitor configuration integrity and electrical properties after
mechanical damage, self-healing supercapacitors are fabricated
by the integration of appropriate self-healing materials into
supercapacitor devices. The first self-healing supercapacitor
was designed by spreading CNT films onto self-healing sub-
strates composed of a supramolecular network (with a low glass
transition temperature below room temperature) and hierarch-
ical flower-like TiO2 nanostructures.347 A PVP–H2SO4 gel served
as both the electrolyte and separator. The interaction between
TiO2 nanospheres and supramolecules by hydrogen bonds held
the shape of the supramolecular networks and enhanced the
glass transition temperature. After cutting, lateral movement of
the underlying self-healing composition layer brings the sepa-
rated areas of the SWCNT layer into contact and restored its
conductivity. In the case of the electrolyte, PVP gel was a self-
adhering material and could self-heal to some extent. When the
device was damaged, the specific capacitance of the 5th healing
was 30 F g1 with the capacitance retention ratio of about 85.7%.
The capacitance of the self-healing supercapacitor decreased
gradually with increasing cycles of cutting and healing. The
ESRs of this supercapacitor before cutting and after the 1st,
3rd and 5th healing were 4.8, 9.8, 13.1, and 15.2 O, respectively.
Compared with the conventional supercapacitor, fiber micro-
supercapacitors are seriously limited by accidental mechanical
damage during practical applications since the reconnection of
the broken fiber electrode composed of multiple tiny fibers
(diameter o20 mm) is much more difficult and challenging.
Fortunately, self-healing fiber supercapacitors were successfully
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developed by wrapping wire-like electrodes around a self-healing
polymer shell.348,349 When the broken parts were brought back
into contact, an aligned-CNT strand was more favorable for the
self-healing of an electrical property. Hydrogen bonds would
be formed between the two sections of the self-healing
polymer fibers, and the aligned CNTs between the two cross-
sections were thus re-connected by van der Waals forces during
the self-healing process of the polymer.348 To improve its
specific capacitance, polyaniline (PANi) was uniformly incorpo-
rated into the aligned CNTs through electropolymerization.
To enhance the reconnection of broken electrodes, magnetic
electrodes (Fe3O4/PPy) with a self-healing polyurethane (PU)
shell were applied to the supercapacitor.349 The strong force
from magnetic attraction between the broken yarn electrodes
benefited reconnection of fibers in the electrodes, enabling
efficient recovery of electrochemical performance after self-
healing. The specific capacitance of the magnetic electrode
was restored to 71.8% after the fourth healing.
A new electrolyte, comprised of polyacrylic acid dual cross-
linked by hydrogen bonding and vinyl hybrid silica nano-
particles (VSNPs-PAA), has been developed for a self-healing
supercapacitor recently.350 This polyelectrolyte had advantages
of tuneable ionic conductivity, self-healability and high stretch-
ability. It was easily self-repaired at room temperature and was
stretched over 3700% without any cracks. During the hydrogen
bond forming process, small conductive CNT patches were
utilized to overcome the well-known misalignment problem
of self-healing supercapacitors. The capacitances from both
CV and charge/discharge curves were maintained completely
during all 20 breaking/healing cycles. This is superior to all the
previous work.347–349 The excellent self-healing property was
attributed to intrinsically self-healable electrolyte and small
CNT patches.
4.6.3 Piezoelectric supercapacitors. In 2006, the report
on piezoelectric ZnO nanowires for electricity generation
attracted substantial attention on piezoelectric materials in
energy harvesting and transducer technology.351 A mechani-
cal-to-electrochemical piezoelectric supercapacitor can be fab-
ricated using a piezoelectric film to replace the traditional
separator of a supercapacitor. However, these inorganic nano-
wire-based electrical generators are fragile to strain. In this
regard, piezoelectric polymers (polyamide (PA) and polyvinyl-
idene fluoride (PVDF) with a predominantly b-phase crystal
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Fig. 16 Schematic illustration of the working principle of piezoelectric supercapacitors driven by compressive straining. Piezoelectric potential can be
created by the mechanical strain along the PVDF film, which will drive anions and cations to migrate towards the interface of the positive and negative
electrode establishing an electronic double layer at the interface.
structure) are promising alternatives for excellent processibility
and flexibility, and low cost.352
The core of a piezoelectric supercapacitor is the piezo-
separator which is normally a well-polarized PVDF film located
between the electrodes. The piezoelectricity originates from
the polar b crystalline phase where the C–F dipoles align in
the same direction and thus produce intrinsic charges.353
In the piezo-electrochemical mechanism, piezoelectric
potential created by the mechanical strain along the PVDF film
can drive anion and cation migration towards the interface of
the positive and negative electrodes establishing an electronic
double layer or pseudo-capacitance at the interface; thus
electricity is therefore stored in the form of electrochemical
energy (Fig. 16). The hybridization of the two separate energy
processes (i.e., mechanically harvesting energy created from a
piezoelectric potential and storing electrochemical energy
induced by ion migration) can supply continuous power by
the mechanical deformation from the environment without
using external DC power.354
Because of their excellent mechanical stability and intrinsic
flexibility, functionalized carbon cloths have been assembled as
both positive and negative electrodes with polarized PVDF films
coated with a H2SO4/PVA electrolyte.355 The maximum specific
capacitance of 357.6 F m2 was obtained at 8 A m2, retaining
59.84% of the capacitance when the current density was increased
to 200 A m2. When the charging process was performed under
a continuous compressive force with the average frequency of
4.5 Hz, the voltage of the piezo-supercapacitor was increased
to 100 mV within 40 s. The stored electric capacity was about
0.25 mA h from the discharge curve at a constant current of
100 mA. The supercapacitor failed to be charged by applying a
repeatable mechanical deformation when replacing the PVDF
film with a commonly used separator without piezoelectric
properties, indicating that the charging of the supercapacitor
was surely a result of the piezoelectric PVDF separator.
The integration of a pseudo-supercapacitor and piezoelectric
materials was achieved using MnO2 nanowires as positive and
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negative electrodes and a PVDF–ZnO film as a separator and a
piezoelectric material.356 The addition of ZnO nanowires in the
PVDF matrix induced the polarization of ions in the composite
film without electrical poling. When applying a compressive
force from continuous palm impact, the voltage of the device
increased from 35 to 145 mV (110 mV charged) in 300 seconds.
The self-charging effect was enhanced with the applied force due
to the increase in piezopotential with the higher applied strain.
A flexible piezoelectric micro-supercapacitor was demon-
strated using a laser engraving technique by integrating a
triboelectric nanogenerator and plane micro-supercapacitor
array into a single device.357 A high degree of integration
was realized through the double-faced laser engraving of a poly-
imide (PI) substrate. The two sides of the graphene electrode
were used separately for fabricating the triboelectric nano-
generator and micro-supercapacitor array. The nanogenerator
component can generate electricity from ambient mechanical
vibrations with high output while the rectified electrical energy
was directly stored in the micro-supercapacitor array compo-
nent, which could be charged to 3 V in 117 minutes.
4.6.4 Shape-memory supercapacitors. Electronic devices that
can be flexible, bendable, foldable and stretchable are desirable
for new applications, such as wearable electronics, smart clothes,
electronic skins, bendable smart phones and implantable medical
devices. This requires electronic devices and their power units
to possess mechanically deformable ability. The appearance of
stretchable, compressible and shape-memory supercapacitor
paves the way to future applications in the above devices. In
2016, there have been several excellent reviews summarizing
the recent progress on flexible, stretchable and compressible
supercapacitors.358–360 Thus, we mainly focus on shape-memory
supercapacitors in this section.
Incorporation of shape-memory materials into supercapaci-
tors can recover devices back to their initial shape or size
after irreversible deformations in practical applications. There
are mainly two categories of shape-memory materials, namely
shape-memory alloys (SMAs) and polymers (SMPs).359,361
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The shape-memory effect of SMAs arises from a reversible
crystalline phase change known as a martensite–austenite
transformation. When heated to a certain temperature, the
deformed SMAs return to their original shape and remove all
plastic deformations. The most prominent SMAs are based on
nickel–titanium (NiTi) due to its superior mechanical and
electrical characteristics.
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A shape-memory supercapacitor was realized using graphene
coated on TiNi alloy flakes as the negative electrode, and an ultrathin
MnO2/Ni film as the positive electrode in gel electrolytes.361 It
demonstrated a specific capacitance of 53.8 F g1 at 0.5 A g1.
The bent device regained its original planar shape within 550 s
when heated to ambient temperature. The recovery speed of
this supercapacitor was relatively low. Recently, NiTi wires were
applied as current collectors and substrates for the active
materials (MnO2 and PPy) in a twisted fiber shape-memory
supercapacitor, which could restore serious plastic deformations
to an undistorted state within a few seconds.362 Meanwhile the
capacitive performance remained nearly unchanged.
Above the glass transition temperature (Tg) (amorphous
polymers) and melting temperature (Tm) (crystalline polymers),
SMPs are soft, light-weight and can be extended to several
hundreds of percent. SMPs can memorize more than one shape
and recover its original form when subjected to various stimuli
such as temperature, light, magnetic fields and electric currents.
Wrapping aligned CNT sheets onto a shape-memory poly-
urethane (SMPU) substrate enabled a shape memory and
fiber-shaped microsupercapacitor.363 After 500 cycles of defor-
mation and recovery at a strain of 50%, its electrochemical
properties showed no obvious decrease, suggesting excellent
stability of the device structure. However, its maximum specific
capacitance was only 42.3 mF cm1, which could be enhanced
by introducing pseudocapacitve materials. Densely compacted
CNT layers and PANi layers were coated on the PVA/CNT SMPU
fibers through layer by layer (LBL) technology.364 The resulting
shape memory supercapacitors not only possessed shape mem-
ory properties, but also exhibited outstanding specific capaci-
tance exceeding 427 F cm3.
4.6.5 Thermal self-protective supercapacitors. When super-
capacitors work at high environmental temperature, the high
power delivery and fast current flow are prone to generate a lot
of heat that the device cannot dissipate quickly which may
result in the risk of fire or explosion. To address the thermal
runaway problem in supercapacitors, a thermal self-protective
supercapacitor was developed in 2013.365 A thermosensitive
polymer P(N-isopropylacrylamide-co-2-acrylamido-2-methyl propane
sulfonic acid) (P(NIPAM-co-SPMA)) was coated onto the surface of
NiAl-layered double hydroxide (LDH) nanowalls as the electrode
material for supercapacitors (Fig. 17a). An increase in temperature
would cause P(NIPAM) to collapse into a hydrophobic state
from its hydrophilic state due to breaking of hydrogen bonds
between N-isopropyl groups and water. The collapsed polymer
at 40 1C inhibits the migration of conductive ions between the
electrodes, thus reducing the specific capacitance (Fig. 17b).
The copolymer poly(N-isopropylacrylamide-co-acrylamide)
(PNIPAM/AM) with LiOH was applied as a reversible sol–gel
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Fig. 17 The working principle of a thermal self-protection supercapacitor
and its electrochemical behavior. (a) Schematic illustration of the
LDH@P(NIPAM-co-SPMA) film on a flexible Ni foil substrate serving as a
self-protection supercapacitor with thermally-responsive ion channels.
(b) The specific capacitance of the switch between 20 1C and 40 1C for
thermal self-protection supercapacitors (modified from ref. 365, copyright
permission from the Royal Society of Chemistry).
electrolyte for thermal self-protective supercapacitors.366
Importantly, the transition temperature of the sol–gel process
could be controlled by adjusting the molar ratio of NIPAM
to AM. The diffusion coefficient of the Li ions decreased from
1.9  1013 m2 s1 at 20 1C to 7.6  1014 m2 s1 at 70 1C.
A Pluronic [poly(ethylene oxide)-block-poly(propylene oxide)-block-
poly(ethylene oxide) (PEO–PPO–PEO)] aqueous solution dissolved
with ions (such as H+ or Li+) was also utilized as a smart electrolyte
for thermal self-protection of supercapacitors.367 The Pluronic-
based electrolyte was in the solution state and the ions could
move freely between the electrodes at room temperature. When
temperature increased, this electrolyte transformed to a gel
state, which would inhibit the motion of ions and shut down
the electrochemical devices. The specific capacitances of the
supercapacitor based on this electrolyte were 110 and 10 F g1
in the sol and gel states, respectively, showing significant
inhibition of its electrochemical storage performance at high
temperature (E91% capacity loss).
4.6.6 Thermal self-charging supercapacitors. Thermal self-
charging supercapacitors were developed to harvest electrical
energy from low-grade heat using thermal-to-electrical energy
conversion techniques, such as the Seebeck effect (electron
diffusion by temperature gradient), thermally driven ion diffusion,
and temperature-dependent electrochemical redox potential.368–372
The thermal self-charging supercapacitor can absorb heat when the
temperature rises and releases electricity during the discharging
process. There are many low-grade heat sources such as the
waste heat in power generation plants, ocean thermal energy,
and distributed solar thermal energy.
The thermal self-charging supercapacitor consisted of two
electrodes at different temperatures. Each electrode was formed
by immersing an electrode in an electrolyte solution.370 At the
electrode–liquid interface, solvated ions were adsorbed and an
electrode potential was developed after the electrical charge/
discharge process (sometimes called activation).373 The adsorp-
tion coverage became different and the electrode potential varied
when temperature changed. With a nickel-coated CNT based
electrode, the thermal sensitivity of the electrode potential was
up to 6 mV K1.374 Meanwhile, the harvested electrical energy
was 600–1800 mJ g1 of electrode material per thermal cycle
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with a temperature range of 45–50 1C.374 Another thermal self-
charging supercapacitor based on PANi@graphene@CNT
employed polystyrene sulfonic acid (PSSH) as both a solid
electrolyte and a voltage generator.369 The Seebeck coefficients
were as high as 8 mV K1. With a small temperature difference
of 5.3 K, a charged potential of 38 mV and an areal capacitance
of 120 mF cm2 were achieved in this supercapacitor. When
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heat was applied to one of the electrodes, the temperature
gradient between the two electrodes caused more mobile H+
ions to diffuse to the cold side (Soret effect), leaving less mobile
PSS ions behind. Therefore, the H+ ion concentration near the
hot electrode decreased and the H+ ion concentration near the
cold electrode increased. As a consequence, the potential
difference between the two electrodes was produced by the
concentration difference according to the Nernst eqn (21):
 þ 
 RT H storage efficiencies currently reach 2.73% and 75.7%, respectively,
Ecell ¼ Ecell  ln  þhot ; (21)
F Hcold
where E is the potential difference between the two electrodes
with temperature gradient; E1 is the standard cell potential
from the two electrodes; the molar concentrations near the hot
and cold electrode are [H+hot] and [H+cold], respectively; R is the
universal gas constant; T is the temperature; and F is the
Faraday constant. The potential difference enables electron
flow leading to oxidation and reduction of PANi at the hot
and cold electrodes, respectively.
The polymer electrolyte based on PEO treated by NaOH
showed an exceptionally high ionic Seebeck coefficient up to
11.1 mV K1.375 The resulting thermal self-charging could convert
and store 2500 times more energy compared with a traditional
thermoelectric generator connected in series with a super-
capacitor. Differently, an open circuit voltage of 80–300 mV was
obtained by heating the commercial EDLCs to 65 1C.373 It was
found that, at higher temperature, the thermo-electrochemical
process could enhance the kinetics of the Faradaic process
including the charge transfer process at the electrolyte/electrode
interface and other processes involved in the reaction (such as
diffusion of reactants in electrolytes). The kinetics of surface
reactions was slower than the free electron flow in the electrode.
The Fermi level of electrons in the negative electrode moved
toward more negative voltages during the thermal charging
process, which led to the increase of the full cell voltage in this
thermal charging process.
4.6.7 Photo self-charging supercapacitors. As the most
widespread, renewable, and environmentally friendly resource
in the world, the solar energy from the sun is estimated to be
3  1024 J year1, which is 104 times more than the consump-
tion rate of mankind. Photovoltaic electricity generation is the
second-fastest growing source in the world’s power sector.
An effective approach to collect the fluctuating electricity
generated from solar cells is to integrate solar cells and super-
capacitors, which is called photo-supercapacitors or photo self-
charging supercapacitors.
The fiber photo-supercapacitors were fabricated by combin-
ing a fiber-shaped dye-sensitized solar cell and a fiber-shaped
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microsupercapacitor into a single device.376–380 For example, a
dye-sensitized solar cell and supercapacitor were integrated by
twisting two fiber electrodes (Ti wire and CNT fiber) together. It
exhibited a high overall photoelectric conversion and storage
efficiency of 1.5%.376 However, due to the use of a liquid
electrolyte, this device exhibited a very low mechanical stability
as two fiber electrodes were peeled off from each other
under bending. Thus a coaxial and all-solid-state ‘energy fiber’
was introduced by integrating polymer solar cells and
supercapacitors.379,380 For the photovoltaic conversion, the
coaxial structure was similar to the efficient planar polymer
solar cell in the radial direction, enabling the generated charges
to be rapidly separated and transported to produce high
photocurrents. For the energy storage, the coaxial structure
brought much higher effective contact area and favors rapid
charge transport.379 The photoelectric conversion and energy
in the CNT@Ti wire based coaxial photo-supercapacitor.380
More importantly, such fiber photo-supercapacitors can be
woven into various structures such as lightweight textiles.
5. Conclusions and outlook
Supercapacitors are emerging as promising devices for electro-
chemical energy storage and this review has introduced recent
progress on theoretical understanding, new electrode materials
and novel device designs of supercapacitors. Research studies
on new materials and devices in supercapacitors are currently
undergoing an exciting development with increasing achieve-
ments. Discovering and creating new materials with tailored
architectures present a chance to improve the performance
with both high power and energy density. MOFs and COFs are
two types of fascinating materials with great potential in the
field of supercapacitors. MXenes and metal nitrides possess
high electronic conductivity. Although investigations have only
been conducted for a short time, MXenes have demonstrated
great potential for enhanced volumetric energy density as
electrodes of supercapacitors. Other layer-structured materials
(like phosphorene) seem to be promising for supercapacitor
applications due to their reduced diffusion pathway and highly
dense structure that induces intercalation chemistry though
they are difficult to synthesize. New reducing agents, etchants,
and intercalants should be considered in the near future.
Recent progress in developing new devices is followed
to reflect a new booming direction in the energy storage
industry. Flow supercapacitors hold great promise for large-
scale stationary energy storage systems, such as smart grids. AC
line-filtering supercapacitors provide a possibility of replacing
aluminum electrolytic capacitors to greatly reduce the sizes of
future electronic circuits and electronic devices. Metal ion
hybrid supercapacitors may be the key to bridge the gap
between conventional metal ion batteries and supercapacitors.
It is worth noting that the present strategies of designing
metal ion capacitors to increase the energy density are usually
realized at the expense of the power capability. The metal ion
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insertion processes into the bulk of the negative electrodes are
known to be substantially more kinetically sluggish than EDLC
in positive electrodes, posing a major challenge to finding
metal ion intercalation pseudocapacitive materials. For micro-
supercapacitors, the unique structures shorten the distance
for ions to travel between electrodes thus enhancing the
electrochemical performance. Various kinds of functions (like
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electrochromism, self-healing, shape-memory, thermal-responsive,
and light) have successfully been introduced into supercapacitors.
This is a great step for achieving smart supercapacitors.
Although some encouraging results have been achieved, the
development of a new generation of supercapacitors is still at
its early stage. Much effort is still needed before real practical
applications become possible: (1) the energy storage mechan-
isms must be deeply understood for controlling interfacial
reactions between the electrode and electrolyte. Advanced
simulation and modeling studies are necessary to uncover
underlying electrochemical mechanisms on the nanoscale.
A lot of theoretical and computational studies on EDLCs have
been reported as discussed in Section 2. However, theoretical
understanding of pseudocapacitance is very limited because
surface redox and ion-intercalation pseudocapacitors are more
complicated and difficult to simulate.381 Besides, the state-of-
the-art in situ microscopic and spectroscopic techniques are
important to provide direct experimental proof. (2) ‘‘Technology
is always limited by the materials available,’’ and this holds true
whether it is in the past, or today, or the future. This call for new
materials has generated a series of new 2D materials beyond
graphene (like germanene, silicone, tinene, and borophene) in
the past several years,382,383 which exhibit potential applications
in supercapacitors due to their unique electronic, chemical, and
surface properties. Of course, one of the greatest challenges for
these new nanomaterials is to achieve a large-scale yield with
high purity. Additionally, for large-scale applications of those
electrode materials discussed in Section 3, more effort should be
made to realize massive production to meet the industry require-
ments. (3) The fast-growing popularity of intelligent electronics
requires the continuous development of smart power sources
with integrated stimulus-response. Integrating more functions
into one energy storage device is fascinating. With further
research effort on the optimization, smart supercapacitors
will play important roles in lightweight, flexible, and wearable
capacitive devices in the near future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Financial support from the National Materials Genome Project
(2016YFB0700600), the Distinguished Young Scientists Program
of the National Natural Science Foundation of China (51425301)
and the NSFC (U1601214, 21374021 and 21210004) is gratefully
appreciated.
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