Received: 30 June 2019 Revised: 6 August 2019 Accepted: 8 August 2019

DOI: 10.1002/inf2.12037

REVIEW ARTICLE

Smart supercapacitors from materials to devices

Rui Wang | Minjie Yao | Zhiqiang Niu

Key Laboratory of Advanced Energy

Materials Chemistry (Ministry of
Abstract
Education), College of Chemistry, Nankai The recent development in smart electronic devices has increased the demand for
University, Tianjin, China
supercapacitors to integrate with other different functions. Recently, many research
Correspondence efforts have been made to fabricate smart components of supercapacitors and to
Zhiqiang Niu, Key Laboratory of Advanced construct them into novel device configurations. In this mini review, we summarize
Energy Materials Chemistry (Ministry of
recent progress in smart supercapacitors with the functions of self-healing, shape
Education), College of Chemistry, Nankai
University, Tianjin 300071, China. memory, electrochromism, and photodetection, including the design of electrode
Email: [email protected] materials, the optimization of the configuration, and working mechanism. Further-
Funding information
more, the perspective and challenges for the development of smart supercapacitors
Ministry of Education of the People's are also discussed deeply.
Republic of China, Grant/Award Number:
B12015; Ministry of Science and KEYWORDS
Technology of People's Republic of China, electrochromism, photodetection, self-healing, shape memory, smart supercapacitors
Grant/Award Number: 2017YFA0206701;
National Natural Science Foundation of
China, Grant/Award Numbers: 21573116,
51602218

1 | INTRODUCTION pseudocapacitors is ascribed to the fast and reversible redox pro-

cess of active materials, such as transition metal oxides/hydrox-
Supercapacitors, also well known as ultracapacitors or electro- ides and conducting polymers.28-30 Thus, pseudocapacitors can
chemical capacitors, have attracted significant interest in both deliver higher specific capacitance, but meanwhile suffer from
academia and industry owing to their high power density, long lower power density, because pseudocapacitive materials usually
cycle life, great stability, and safety.1-11 Their electrochemical possess low conductivity. Consequently, the pseudocapacitive
properties can fill the gap between conventional plane-parallel materials are often composited with carbon materials with electri-
capacitors and batteries. Depending on the energy storage mech- cal double layer capacitance to improve the overall performance
anism and active materials, supercapacitors can be distinguished of electrodes.
into two categories: electrochemical double layer capacitors Recently, various smart electronic devices with different
(EDLCs) and pseudocapacitors.2,12-18 The capacitance of functions, such as self-healing, shape memory, electro-
EDLCs is attributed to the electrical charge storing at the elec- chromism, and photodetection, have been developed.31-33 In
trode/electrolyte interface, which is only a physical process with- order to further integrate these advanced electronic devices
out faradaic reactions. Therefore, EDLCs can achieve fast with their power sources into self-powered smart electronic
charging/discharging rates and excellent cycling perfor- devices, smart supercapacitors have to be considered. How-
ever, conventional supercapacitor devices cannot match the
mance.3,19-27 However, the energy density of EDLCs is relatively
demand of these smart supercapacitor devices due to the limi-
low, owing to the incomplete contact between porous electrodes
tation of electrode and electrolyte materials as well as the
and electrolyte. Different from EDLCs, the capacitance of
device configurations.34 Therefore, the successful assembly of
Dedicated to 100th Anniversary of Nankai University. smart supercapacitors depends mainly on the fabrication of
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original
work is properly cited.
© 2019 The Authors. InfoMat published by John Wiley & Sons Australia, Ltd on behalf of UESTC.

InfoMat. 2020;2:113–125. wileyonlinelibrary.com/journal/inf2 113

114 WANG ET AL.

FIGURE 1 Schematic of the smart supercapacitors with the

functions of self-healing, shape memory, electrochromism, and F I G U R E 2 A, Schematic diagram of energy storage mechanism
photodetection of EDLCs. B, Device configurations of film, fiber, and micro-
supercapacitors.2 EDLC, electrochemical double layer capacitor

innovative electrode and electrolyte materials and the design

of unconventional device configurations. The electrode and species in the diffuse layer can be simulated through the
electrolyte materials of smart supercapacitors should not only Stern model. The total capacitance (Ct) of the electrode can
possess large surface area and high conductivity but also dis- be summarized as the following equation:
play smart behaviors. Meanwhile, the configurations of smart
1 1 1
supercapacitors have to be simplified to move toward light, = + ð1Þ
thin, flexible, and integrated. Ct CH CD
Recently, a variety of smart supercapacitors have been
where CH and CD refer to the capacitances at the Helmholtz
successfully designed and fabricated by developing novel
layer and the diffuse layer, respectively. Generally, nano-
functional component materials and device configurations.
carbon materials, such as active carbon, carbon nanotubes
In this review, we will present the recent developments in
(CNTs), and graphene, are the most widely used materials
smart supercapacitors with self-healing, shape memory, elec-
for EDLCs, because they possess advantages of large surface
trochromism, and photodetection functions (Figure 1). The
area, high electrical conductivity, and electrochemical
fundamental principles and main characteristics of these
stability.
smart supercapacitors will be discussed in detail. Finally, the Compared with EDLCs, the capacitance of pseudo-
challenges and further prospects of smart supercapacitors are capacitors is attributed to the fast and reversible redox pro-
discussed. cess occurring between active materials and electrolyte. As a
result, pseudocapacitors can deliver much higher capacitance
2 | T HE MECHANI SM OF than EDLCs. The most common pseudocapacitive materials
SUPERCAPACITORS are conductive polymers (polyaniline [PANI], polypyrrole
[PPy], and so on) and transition metal oxides/hydroxides
The capacitance of EDLCs arises from the reversible electri- (RuO2, MnO2, Co(OH)2, and so on). The simplified equa-
cal charge accumulation on the surface/interface of elec- tion for their reaction processes is expressed as follows:
trode, which is mainly dependent on the specific surface
area of the electrode materials. When a potential difference Mn + + xe − $ Mðn− xÞ + : ð2Þ
is applied between two electrodes, the cations and anions in
electrolyte will move toward the surface of negatively polar- For conductive polymers, a reversible transfer of ions
ized electrode and positively polarized electrode to balance between polymer backbone and electrolyte occurs rapidly
the electrons and holes, respectively (Figure 2A). The accu- during the oxidation and reduction processes. The selection
mulation of ions on electrode surface and the motion of ionic of potential window in this process is extremely important to
WANG ET AL. 115

use conductive polymers as electrode materials, because they are integrated on them. The electrolyte is subsequently
will be easily degraded beyond the suitable potential win- coated on the top of devices to ensure ion transport between
dow, or to switch to an insulating state when the potential is electrodes. The total size of micro-supercapacitors could be
too negative. Different from conductive polymers, metal sites in the millimeter scale. By selecting suitable components,
in transition metal oxides/hydroxides usually act as redox- smart micro-supercapacitors can be rationally designed. Fur-
active centers to realize different valence states. Although thermore, the micro-structure in supercapacitors will shorten
they have lower conductivity in comparison with conductive the ion diffusion distance in electrolyte, resulting in an effec-
polymers, they can display better electrochemical stability tive utilization of the special surface area of micro-elec-
than conductive polymers. Active materials with pseudo- trodes. Moreover, the opened side edges of micro-electrodes
capacitance are often added into carbon materials to improve are also exposed to the electrolyte, which is beneficial for
the overall capacitance of the electrode materials through the electrolyte to infiltrate into the micro-electrodes and leads to
synergistic effects between them. high energy density. Compared with other configurations of
supercapacitors, micro-supercapacitors can be easily inte-
grated onto one chip and can be compatible with other
3 | T HE DEV I C E CON F I GU R A T I O N S
micro-electronic devices, possessing potential for working
OF SUPERCAPACITORS
as smart power sources of portable micro-electronic devices.
Compared with traditional 2D planar supercapacitors, fiber
The achievement of smart supercapacitors usually depends on
supercapacitors are usually shaped like 1D wires with diame-
the design of their configurations. However, conventional
ters ranging from micrometer to millimeter. There are three
supercapacitors are mainly designed in button cells or spiral-
main configurations of fiber supercapacitor devices: coaxial,
wound configuration, which are too bulky and heavy to serve
twisted fibers, and all-in-one fiber supercapacitors. The coax-
as smart energy storage devices. Different from the case of
ial fiber supercapacitors are usually fabricated by layer-by-
conventional supercapacitors, several film, fiber, and micro-
layer assembling core fiber electrode, separator or solid-state
sale supercapacitor configurations have been developed to meet
electrolyte, and electrode shell together. Based on this config-
the demand of smart energy storage devices in recent years
uration, a self-healing fiber supercapacitor was fabricated,
(Figure 2B).
where self-healing substance served as core and aligned CNTs
The development in smart electronic devices has
acted as electrodes. Different from coaxial case, the twisted
increased the demand for their power source, such as shape
fiber supercapacitors can be obtained by twisting two fiber
memory and electrochromic supercapacitors, to be thin, flex-
electrodes with a separator or solid-state electrolytes between
ible, and even foldable. Generally, film supercapacitors are
them. Most of the smart fiber supercapacitors are designed in
fabricated in a sandwiched configuration, where all compo-
this configuration, because it can be easily integrated with
nents are designed in ultrathin thickness and often possess
other fiber-shaped electronic devices, such as sensors or solar
excellent flexibility. Furthermore, the metal current collec-
cells, to achieve multifunctional systems. Furthermore, owing
tors are usually removed by increasing the conductivity of
to the unique wire-shaped structure, fiber supercapacitors can
electrode materials. However, traditional liquid electrolyte
be woven into fabrics or textiles, which exhibits great pros-
would suffer from leakage during bending or twisting, lead-
pect for acting as wearable energy storage devices. Recently,
ing to possible safety problem and harm for environment.
an integrated energy wire has been developed to simulta-
Therefore, solid- or quasi-solid-state electrolytes are highly
neously realize energy storage and photoelectric conversion
desired for film supercapacitors. The solid- or quasi solid-
with high efficiency.36 Aligned CNT fibers were twisted with
state electrolytes with ultrathin thickness will not only
the modified Ti wire to act as fiber substance, and photoactive
reduce the ion transport distance, but also work as a separa-
materials were then deposited onto the TiO2 nanotube-
tor to further simplify the configuration of devices. Recently,
modified parts on the Ti wire to achieve photoelectric conver-
a solid-state film electrochromic supercapacitor with highly
sion. For all-in-one fiber configuration, the micro-electrodes
transparent Ni(OH)2-polyethylenimine ethoxylated (PEIE)/
are prepared onto one fiber and then the electrolyte is coated
poly(3,4-ethylenedioxythiophene): polystyrene sulfonate
on them. However, the complicated preparations usually limit
(PEDOT: PSS) electrodes was fabricated.35 Owing to the
their combination with other smart functions.
thin thicknesses of electrodes, the device demonstrated a
high transparency and excellent coloration efficiency.
In addition, miniaturizing energy storage devices onto a 4 | SELF-HEALING
chip will effectively increase the energy density of devices. SUPERCAPACITORS
Micro-supercapacitors generally consist of interdigital con-
ductive substrates as current collectors, and several finger Flexible supercapacitors with different configurations have
electrodes sequestered from each other by an insulating gap been developed and can often endure some bending or
116 WANG ET AL.

stretching strains to a certain extent.37 However, they will flower-like TiO2 nanospheres and a supramolecular network
suffer undesirable mechanical damage under large internal in 2014 (Figure 3A).44 As there were a large amount of hydro-
or external deformation, resulting in the degradation of elec- gen bond acceptors and donors in the supramolecular network,
trochemical performance and serious safety problems due to when damaged, the substrate could re-form dynamical chain
the leakage of electrolyte.38 If supercapacitor devices have and cross-links between the fractured surfaces. Furthermore, in
the ability to automatically repair their damage, they will this case, single-walled carbon nanotubes (SWCNTs) networks
recover the original performance or minimize the perfor- that were spread onto such self-healing substrate were used as
mance degradation of the supercapacitors. As a result, the both electrodes of supercapacitors. Along with the restoration
durability and lifetime of self-healing supercapacitors will be of substrate, the SWCNT network electrodes could also be
significantly enhanced and prolonged, further reducing elec- interconnected simultaneously again. Therefore, the super-
tronic waste and economic cost.39-43 In this regard, various capacitor demonstrated a high capacity retention rate of 85.7%
self-healing materials, especially polymers, are introduced even after five cutting/healing cycles. In addition, based on a
to design and assemble self-healing supercapacitors. These similar self-healing polymer, a healable polymer fiber was
self-healing polymers generally contain highly reversible developed in 2014, where aligned CNTs can be assembled onto
dynamic chemical and physical cross-linked bonds, which its surface, acting as the seal-healing supercapacitor electrodes
can respond to external physical stimuli, such as light, tem- (Figure 3B).45 Apart from this type of self-healing polymer, car-
perature, and pH, to achieve self-healing ability. boxylated polyurethane (PU) is also a common self-healing
The first self-healing supercapacitor was achieved by material.34 By coating the PU layer onto the surface of spring-
designing a self-healing substrate composed of hierarchical shaped reduced graphene oxide (rGO)-based supercapacitors,

FIGURE 3 A, Schematic of the fabrication of planar self-healing supercapacitor by spreading SWCNTs electrodes onto self-healing
substrates. Reproduced with permission.44 Copyright 2014, Wiley-VCH. B, Schematic of the self-healing of fiber-shaped electrodes. Reproduced
with permission.45 Copyright 2014, Wiley-VCH. C, Optical images of the healing process of a 3D self-healing micro-supercapacitor. Reproduced
with permission.46 Copyright 2018, American Chemical Society. D, Relaxed and elongated state of the self-healing gel polymer electrolyte based on
VSNPs-PAA. E, Schematic of the origin of stretchability. Reproduced with permission.47 Copyright 2015, Nature Publishing Group. F, Schematic
of the healing mechanism of GCP@PPy hydrogel stimulated by NIR laser or electricity. Reproduced with permission.48 Copyright 2019, Wiley-
VCH. G, Optical images of tailoring omni-healable supercapacitor into an H-shaped pattern. H, Cyclic voltammetry curves at 100 mV s−1. I,
Galvanostatic charge/discharge curves at 1.0 A g−1 of the omni-healable supercapacitor before and after tailoring. Reproduced with permission.49
Copyright 2017, Wiley-VCH. SWCNT, single-walled carbon nanotube; VNSP-PAA, polyacrylic acid and hybrid vinyl-silica nanoparticles
WANG ET AL. 117

another self-healing device was obtained in 2017.50 Accompa- and the interfaces between them possessed the ability of omni-
nied with the high mechanical strength of PU, the fiber-shaped directional healing. Interestingly, the supercapacitor could also
supercapacitors exhibited 54.2% and 82.4% capacity retention be tailored into different small geometric shapes, which could
after third healing and a high stretch of 100%, respectively. Sim- be healed into new patterns with electrochemical performance
ilarly, a PU shell endowed the 3D MXene-rGO composite- mainly unchanged.
based micro-supercapacitors with a self-healing ability in 2018
(Figure 3C).46 Such micro-supercapacitors exhibited a high spe-
5 | SHAPE MEMORY
cific area capacitance of 34.6 mF cm−2 at 1 mV s−1 and 81.7%
SUPERCAPACITORS
capacitance retention after five healing process.
Gel or hydrogel electrolytes often possess excellent physical
Supercapacitors will undergo diverse irreversible deformations
flexibility and excellent electrochemical properties, where poly- during the practical application, which easily cause structural
mer is the critical component.5 The traditional poly(vinyl alco- and functional damage on account of the long-term stress.53
hol) (PVA)- or poly(vinyl pyrrolidone) (PVP)-based gel After introducing shape memory function, the potential fatigue
electrolytes can autonomously self-heal, because there are of supercapacitors will greatly recover, thus prolonging the
O-HO hydrogen bonds between the polymer chains.51 How- cycling life of devices. Recently, various shape memory elec-
ever, these gel electrolytes are formed without cross-linking, tronics have been developed. To meet the demand of these elec-
resulting in an unsatisfactory healable and mechanical proper- tronics and achieve shape memory electronic systems, shape
ties. To further enhance the self-healing ability of gel electro- memory supercapacitors have to be considered. It is noticed that
lytes, a novel gel polymer electrolyte that consisted of appropriate shape memory materials, which can respond to
polyacrylic acid and hybrid vinyl-silica nanoparticles (VSNPs- external stimuli, such as temperature, pressure, and magnetic
PAA) was prepared successfully in 2015 (Figure 3D,E).47 force, are the key component for designing such smart super-
Owing to the unique structure of polyacrylic acid cross-linked capacitors. Typically, they can be classified into two types: shape
by vinyl hybrid silica nanoparticles and hydrogen bonds, such memory alloys (SMAs) and shape memory polymers (SMPs).54
an electrolyte could be highly healable and stretchable, even up For SMA materials, shape memory effect is realized through
to >3700%. The supercapacitors based on this electrolyte dem- a reversible crystalline phase change called as a martensite-
onstrated nearly 100% capacitance retention after 20 cutting/ austenite transformation.33 When heated to a certain tempera-
healing cycles. Different from the cross-link between polymer ture, the deformed SMAs will return to their original shape and
molecules in the above-mentioned hydrogel electrolytes, a all plastic deformations will be removed. There are four major
hydrogel cross-linked by double linkers of Laponite and types of SMAs, including NiTi-based, Cu-based, Fe-based, and
graphene oxide was developed and applied in self-healing intermetallic compounds.55 Among them, NiTi is the most
supercapacitors in 2019.52 The functional groups, such as prominent SMAs for supercapacitors due to its superior mechan-
COOH, OH, and Mg2+, in Laponite and GO will efficiently ical and electrical characteristics. A shape memory super-
cross-link CONH2 in polymer chains, resulting in outstanding capacitor was fabricated by using graphene coated on NiTi alloy
mechanical stretchability and healing performance. flakes as the negative electrode and an ultrathin MnO2/Ni film as
As the fabrication of hydrogel electrolyte is a process of con- the positive electrode in 2016, respectively (Figure 4A,B).56 The
verting liquid to hydrogel state, other components such as cath- bent device was able to recover to its original planar shape within
ode, separator, and anode could be integrated together by the 550 seconds under the ambient temperature. Interestingly, the
hydrogel electrolyte through adjusting the supercapacitor config- NiTi-based supercapacitors could be assembled into a watch-
uration and the gel process. The integrated structure will be bene- band and automatically wrapped the human wrist when touching
ficial to the seal-healing of whole devices. For instance, a the human body, suggesting the potential applications of shape
real-time omni-healing all-gel-state supercapacitor was fabricated memory supercapacitors in wearable electronic devices. How-
in 2019 (Figure 3F).48 The GCP@PPy hydrogel electrode and ever, the recovery speed of such a shape memory supercapacitor
the CP hydrogel electrolyte were chemically cross-linked with is relatively low, probably because of the stress from the positive
gold nanoparticles. As a result, the supercapacitor exhibited a electrode. In addition, fiber-shaped shape memory super-
superhigh stretching strain of 800% and displayed a timely elec- capacitors possess more design versatility and potential in wear-
trical healability with efficiency of 80% within 2 minutes. Simi- able electronic devices because of their 1D structure and the
larly, an omni-healable supercapacitor that could recover its possibility of bending to any shape.59 In this case, NiTi wires
configuration and electrochemical and mechanical performances were used as current collectors in a twisted wire-shaped super-
concurrently has also been reported in 2017 (Figure 3G-I).49 capacitor in 2016.60 The shape recovery process of this sup-
The electrodes and electrolyte were integrated together owing ercapacitor was completed within 25 seconds with 96%
to a PVA-g-TMAC/KCl polymer electrolyte cross-linked via capacity retention. After 15 deformation-restoration cycles,
diol-borate ester bonds. Therefore, electrodes and electrolyte the supercapacitor recovered 85% of original shape and 86% of
118 WANG ET AL.

FIGURE 4 A, Schematic of the configuration of shape memory supercapacitor based on NiTi foil. B, Optical images of the fabrication of
shape memory supercapacitor and the flexibility of electrode. Reproduced with permission.56 Copyright 2016, Wiley-VCH. C, Cross-sectional
scanning electron microscopy image of the graphene/carboxylated polyurethane (PU) composite film. Reproduced with permission.57 Copyright
2012, Elsevier. D, Schematic of the fiber-shaped shape memory supercapacitor and the resulting textile that can reversibly transformed into flexural
or elongated states. E, Dependence of the specific capacitance on deformation cycle number. F, Galvanostatic charge/discharge curves of the fiber-
shaped shape memory supercapacitor under a dynamic shape-recovering process at a current density of 0.2 A g−1. Reproduced with permission.58
Copyright 2015, Wiley-VCH

initial capacitance. The supercapacitors were readily woven into utilized as the smart substrate of shape memory supercapacitors
traditional fabrics to make a smart sleeve, which can memorize in 2015. After coating CNTs and PANI as active materials, the
its predesigned shape and automatically self-curl to realize heat resultant supercapacitors not only possessed shape memory
dissipation and cooling when the human body is too hot. properties, but also exhibited outstanding energy storage perfor-
SMPs such as polyurethane, polynorbornene, trans-iso- mance, with the capacitance of ~427 F cm−3.62 Similarly, a
polyprene, and styrene-butadiene copolymers display lighter shape memory fiber supercapacitor was obtained by sequen-
weight in comparison with SMAs.61 Moreover, after adding dif- tially coating thin layers of CNTs, PVA gel electrolyte, CNTs,
ferent reversible phase transitions into the polymers, SMPs can and PVA gel electrolyte on a PU fiber in 2015 (Figure 4D-F).58
memorize more than one shape and recover their original state In addition to its flexibility and stretchability, the supercapacitor
in a single shape memory cycle when subjected to various stim- can be transformed and “frozen” into user-required shapes and
uli, such as temperature, light, magnetic fields, and electric cur- sizes. Furthermore, it can recover to the original shape and size
rents.55 Therefore, SMPs are recently used in shape memory
automatically once the temperature exceeds the thermal transi-
supercapacitors. PU is a common SMP. A bilayered composite
tion temperature.
film that was fabricated by coating graphene paper onto the PU
film displayed excellent shape memory behavior in 2012
(Figure 4C).57 The composite film could be changed into vari- 6 | ELECTROCHROMIC
ous shapes at 80 C and recover to the original shape at room SUPERCAPACITORS
temperature less than 1 second, exhibiting excellent shape
recovery ability. In addition to graphene, PU reinforced with Electrochromic materials possess the ability to alter their
CNTs has also been fabricated via wet-spinning and was colors reversibly through charge insertion/extraction or
WANG ET AL. 119

chemical reduction/oxidation.63 If electrochromic materials working mechanism of WO3 can be summarized as in the
can serve as the components of supercapacitors, the super- following equation:
capacitor will store energy and meanwhile accurately sense
energy variations according to their visible color change.64 WO3 ðbleachedÞ + H + + e − $ HWO3 ðcoloredÞ: ð3Þ
Therefore, introducing electrochromic behaviors into super-
capacitors has attracted much attention. The common elec- WO3 films have been deposited on fluorine-doped tin
trochromic materials include various transition metal oxides, oxide (FTO) glass as electrodes for supercapacitors in 2014,
conducting polymers, and metal organic frameworks. Some which exhibited a high specific capacitance of 639.8 F g−1
of these materials can also act as the electrodes of super- and excellent electrochromic properties (Figure 5C).67 Their
capacitors. As a result, based on them, various electrochromic color varied from transparent to deep blue, and an abrupt
supercapacitors were designed. decrease could be observed in optical transmittance from
Transition metal oxides were first applied in elec- 91.3% to 15.1% at a wavelength of 633 nm from 0 to −0.6 V
trochromic electronic device. Among them, tungsten oxides (vs Ag/AgCl). However, the above-mentioned system does
are the most common electrochromic materials, in which the not show photoresponsiveness, resulting in the lack of auto-
proton insertion/extraction induces a color change.65 The matic adjustment of sunlight. The electrochromic system with

FIGURE 5 A, Schematic of the fabrication and electrochromic processes of the electrochromic micro-supercapacitor. B, Optical images of the
transmittance of electrochromic micro-supercapacitor under different charging states. Reproduced with permission.66 Copyright 2018,
Wiley-VCH. C, Cross-sectional scanning electron microscopy image of the WO3 thin film evaporated on a fluorine-doped tin oxide (FTO) substrate.
Reproduced with permission.67 Copyright 2014, Wiley-VCH. D, Cyclic voltammetry curves of the PANI film, W18O49 nanowire film, and hybrid
smart supercapacitor electrode at a scan rate of 10 mV s−1.E, Optical images of the electrochromic performance of W18O49-PANI electrode at
different potentials. Reproduced with permission.68 Copyright 2014, American Chemical Society. F, In situ optical transmittance spectra for a
PEDOP-Au@WO3 film. Reproduced with permission.69 Copyright 2015, Wiley-VCH
120 WANG ET AL.

the adaptive modulation of transmittance in response to inci- are yellow-to-green in the undoped insulating state and blue-to-
dent sunlight will be useful in wearable electronics and archi- violet in the doped conductive state.76
tecture, where the devices can reversibly change their color Compared with utilizing single active material, combining
and reliably store energy. An integrated device with solar sen- various electrochromic materials into one smart electrode of
sor and electrochromic supercapacitor based on WO3 was supercapacitor will widen the potential window and respond
developed in 2017. It could intelligently change color only in to different energy storage levels. A smart supercapacitor
response to high intensity incident light, thereby achieving electrodes based on W18O49-PANI layers were fabricated by
optimized energy saving.70 The fabricated device illustrated a combining photolithography with electrodeposition in 2014
high coloration efficiency of 64.8 cm2 C−1 and specific capac- (Figure 5D,E).68 Both W18O49 and PANI displayed various
itance of 406.0 F g−1. Moreover, it could also maintain 97.6% color changes in different potential windows of −0.5 to 0 V
of electrochromic capability. (W18O49) and 0 to 0.8 V (PANI). When one component is
Besides tungsten oxides, other transition metal oxides such transparent, the other component is colored, detecting the
as V2O5 and NiO have also been utilized in electrochromic energy changes. In addition, poly(3,4-ethylenedioxypyrrole)
supercapacitors. A stimulus-responsive supercapacitor that (PEDOP) is also a promising electrochromic polymer owing
consisted of gyroid structured V2O5 electrodes was success- to its low oxidation potential (Figure 5F).69 A PEDOP-
fully fabricated in 2012.71 Owing to the interconnected porous Au@WO3 electrode of supercapacitor was designed with
network in electrodes, the lithium ion intercalation/extraction capability of optically modulating solar energy in 2015. When
and faradaic reactions in electrodes are fast and efficient. the potential varied from −1.5 to 1.5 V, the hybrid electrode
Therefore, the supercapacitor displayed a rapid color change demonstrated a gradual optical transition from red-blue to
from green to yellow with a high capacitance of 155 F g−1. blue-grey with a coloration efficiency of 707 cm2 C−1 and
Similarly, a nano-generator and an electrochromic micro-sup- switching time of about 6 seconds.
ercapacitor-integrated device were reported in 2018, where
AgNWs/NiO on ITO electrodes worked as both elec- 7 | PHOTODETECTABLE
trochromic and capacitive materials for supercapacitor SUPERCAPACITORS
(Figure 5A,B).66 During the charging/discharging process, the
positive electrodes in micro-supercapacitor turned to dark The photodetectors are able to convert light into electrical sig-
color and recovered to be transparent due to the reversible far- nal, which have extensive applications in many fields, such as
adaic redox process of Ni2+/Ni3+ couple. environmental monitoring and sensors.77,78 However, tradi-
However, electrochromic transition metal oxides have some tional photodetectors are often powered by external power
drawbacks, such as heavy weight, slow switching times, and sources, which will decrease the energy density of the whole
poor coloration efficiencies. In order to overcome the above- electronic system and seriously limit their flexibility. Integrat-
mentioned problems, conducting polymer materials have been ing energy storage device and photodetectors together will
developed to serve as novel electrochromic materials.72 PANI endow the devices with compact configurations. Recently,
has been widely utilized as the active electrode materials of different integrated systems with supercapacitor and photode-
supercapacitors. Combining with the electrochromic behavior, tectors have been designed. Furthermore, in some case, their
PANI film electrodes can demonstrate reversible color changes capacitance and photodetection behaviors can remain stable
from transparent (leucoemeraldine) to yellow-green (emeraldine) even under flexible states.
and further to dark-blue-black (pernigraniline) during the poten- TiO2 nanoparticles are widely utilized in the field of photo-
tial from −0.2 to +1.0 V vs SCE.73 A new multifunctional electrochemical devices due to their high effectiveness, low
device integrating solar cell and supercapacitor with elec- cost, and chemical stability.79 Carbon materials possess conju-
trochromic function based on ordered PANI nanowire array gated π systems that can induce the synergistic effects between
electrodes was first fabricated in 2012 and named as “ESS win- them and metal oxides.80 Inspired by this, TiO2 nanoparticles
dow.”74 The ESS window exhibited high stability as a super- were coated onto the SWCNT film to serve as supercapacitor
capacitor, and in situ optical measurements proved its electrodes and the working electrode of the photodetector in
electrochromic function. Similarly, a fiber-shaped electrochromic 2017 (Figure 6A-C).81 Based on SWCNT films with TiO2
supercapacitor was developed in 2014, where aligned CNTs nanoparticles, the foldable all-solid-state paper-like integrated
were wound onto a stretched elastic fiber, and PANI was then device with supercapacitor and photodetector functions was
electrodeposited to prepare CNT/PANI composite electrodes.75 fabricated in a simplified and compact configuration. It deliv-
The supercapacitor demonstrated rapid and reversible chromatic ered outstanding specific capacitance and power density. More-
transitions between blue, green, and light yellow during the over, when exposed to the UV light with an intensity of
charge/discharge processes. Apart from PANI, PPy also possess 40 mW cm−2, the integrated device showed excellent sensitivity
electrochromic and electrochemical properties. Thin PPy films of detecting photocurrent about 2.77 μA and sensitivity of 38.5.
WANG ET AL. 121

F I G U R E 6 A, Schematic of a supercapacitor integrated with photodetector. B, Normalized sheet resistance of SWCNT film and TiO2 NPs-
coated SWCNT film on the paper at varied folding levels. C, The sensitivity of integrated device as photodetector at varied folding angle.
Reproduced with permission.81 Copyright 2016, Wiley-VCH. D, Schematic of the mechanism of integrated device. E, Current response of the
photodetector under different incident light intensities. Reproduced with permission.82 Copyright 2014, Wiley-VCH. F, Discharging current
response by exposure to different incident light intensities. Reproduced with permission.83 Copyright 2016, Wiley-VCH

Furthermore, the capacitance of this device is almost unchanged on carbon fibers was designed and assembled into a super-
even under 180 bending or folding 200 times, suggesting that capacitor in 2016, which was electrochemically active for
the integrated device can act as a flexible energy storage device. energy storage and meanwhile sensitive to light illumination
Such integrated devices will pave the way for assembling (Figure 6F).83 The visible light is detected by monitoring the
energy storage devices and other electronics with high flexibil- change of discharging current and the light response, and
ity and stable electrochemical performance. relaxation time is less than 7.5 seconds.
Apart from film devices, a fiber-based flexible asymmet-
ric supercapacitor was also fabricated based on titanium
wire/Co3O4 nanowires as positive electrode and carbon 8 | CONCLUSION AND
fibers/graphene as negative electrode in 2014 (Figure 6D, PERSPECTIVE
E).82 Upon the absorption of light, the electron-hole pairs
generated in the graphene will be separated by an external In addition to energy storage behavior, smart supercapacitors
field. The electrons move to the positive Co3O4 electrode, can also possess the capability of self-healing, shape mem-
while the holes to the negative graphene electrode, resulting ory, electrochromism, and photodetection. These additional
in an improved supercapacitor leakage current to detect the abilities extend the application fields of supercapacitors.
light. Similarly, WO3,84 ZnO,85 and Fe2O386 are also both Various smart supercapacitors have been developed by
photoresponsive and electrocapacitive, and they have been designing the electrodes and electrolytes of the super-
utilized to design photodetectable supercapacitors. Con- capacitors as well as simplifying the device configurations.
ducting polymers are also promising candidate of bifunc- This review summarizes the development of smart super-
tional electrodes. In comparison with traditional inorganic capacitors with self-healing, shape memory, electro-
compounds, conducting polymers possess the advantages of chromism, and photodetection. Furthermore, their working
low cost and high electrical conductivity. In addition, their mechanism and performance are discussed in detail.
photodetection properties can be modified by the rational Although a great amount of progress has been made in
design of molecules, which will improve their energy con- the fabrication of smart supercapacitors, there is still much
version efficiency and sensitivity to light. As a proof of con- work to be done in self-healing, shape memory, elec-
cept, a multifunctional electrode of electropolymerized PPy trochromic, and photodetection supercapacitors:
122 WANG ET AL.

1. The recent research about self-healing supercapacitors ACKNOWLEDGMENTS

focuses more on the healing of independent electrodes or
This work was supported by Ministry of Science and Tech-
electrolytes. However, the self-healing ability of some
nology of China (2017YFA0206701), National Natural Sci-
reported electrodes or electrolytes is not satisfactory and
ence Foundation of China (21573116 and 51602218), and
requires external stimuli, such as light and heat, to accel-
Ministry of Education of China (B12015).
erate the healing process. Moreover, the all-in-one con-
figuration, where all their components are integrated
together, is also highly desired for self-healing super- C O N F L I C T O F I N T ER ES T
capacitors, because their continuous seamless configura-
tions could effectively enhance the self-healing ability of The authors declare no conflict of interest.
whole devices. Furthermore, the all-in-one super-
capacitor devices are capable of avoiding relative dis- OR CI D
placement or detachment between their neighboring
components under repeated self-healing process. Zhiqiang Niu https://orcid.org/0000-0001-9560-7283
2. The design of shape memory supercapacitors is still at a
very primary stage with many opportunities to be
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Rui Wang received his B.S. degree in
4-ethylenedioxypyrrole)–au@WO3-based electrochromic pseudo-
capacitor. ChemPhysChem. 2015;16:377-389.
chemistry from Nankai University in
70. Yun TG, Kim D, Kim YH, Park M, Hyun S, Han SM. Photo- 2018. He then joined the Key Labora-
responsive smart coloration electrochromic supercapacitor. Adv tory of Advanced Energy Materials
Mater. 2017;29:1606728. Chemistry in Nankai University under
71. Wei D, Scherer MRJ, Bower C, Andrew P, Ryhänen T, Steiner U. the supervision of Prof. Zhiqiang Niu.
A nanostructured electrochromic supercapacitor. Nano Lett. 2012; His research focuses on the develop-
12:1857-1862.
ment for multifunctional smart supercapacitors.
72. Sonmez G, Sonmez HB, Shen CKF, Wudl F. Red, green, and blue
colors in polymeric electrochromics. Adv Mater. 2004;16:
Minjie Yao received her B.S. degree in
1905-1908.
73. Kobayashi T, Yoneyama H, Tamura H. Polyaniline film-coated chemistry from Zhengzhou University
electrodes as electrochromic display devices. J Electro Chem. in 2016. She then joined the Key Labo-
1984;161:419-423. ratory of Advanced Energy Materials
74. Wang K, Wu H, Meng Y, Zhang Y, Wei Z. Integrated energy stor- Chemistry in Nankai University under
age and electrochromic function in one flexible device: an energy the supervision of Prof. Zhiqiang Niu.
storage smart window. Energ Environ Sci. 2012;5:8384-8389. Her research focuses on the design and
fabrication of novel flexible energy storage devices.
WANG ET AL. 125

Zhiqiang Niu is a Professor at the 90 peer-reviewed journal papers. His research interests
College of Chemistry, Nankai Univer- include advanced energy storage materials and devices.
sity. He received his Ph.D. degree from
the Institute of Physics, Chinese Acad-
emy of Sciences in 2010. After his post-
doctoral research in the School of
Materials Science and Engineering,
How to cite this article: Wang R, Yao M, Niu Z.
Nanyang Technological University (Singapore), he started
Smart supercapacitors from materials to devices.
his independent research career in Nankai University in
InfoMat. 2020;2:113–125. https://doi.org/10.1002/
2014. He has been awarded the National Youth Thousand
inf2.12037
Talents of China (2015). He has published more than