2021ReviewG-MSCsente 202000844

REVIEW
www.entechnol.de
Recent Progress in Graphene-Based Microsupercapacitors

Balakrishnan Kirubasankar, Balakrishnan Balan, Chao Yan, and Subramania Angaiah*
pseudocapacitors.[13–17] The electrode

The fast growing field of microsized electronic devices has urgent demand for materials such as activated carbon, carbon
next-generation microscale, flexible, and lightweight energy conversion and nanotubes (CNTs), and graphene show a
storage devices. Among the various microdevices, microsupercapacitors (MSCs) non-Faradaic mechanism which comes
under the EDLC category.[18–20] On the con-
are a promising energy storage device due to their fast rechargeability, better rate
trary, electrode materials such as transition
capability, long cycle life, and ultrahigh power density. The 2D graphene pos- metal oxides (TMOs)/transition metal
sesses a large surface area with flexibility, better conductivity, transparency, and hydroxides (TMHOs) (RuO2, MnO2,
high quantum capacitance that lead to an ideal energy storage material for the Co3O4, NiCo2O4, Ni(OH)2, Co(OH)2,
MSCs. Therefore, this review aims to summarize recent advances in graphene- etc.),[21–38] conducting polymers (CPs) (pol-
yaniline [PANI], polypyrrole [PPy], PTh,
based MSCs. A particular emphasis is put on the various fabrication technologies
poly(3,4,-ethylenedioxythiophene)
for MSCs such as printing, laser, wet-spin, and photolithography technique that [PEDOT]),[39–46] transition metal chalcoge-
are discussed elaborately. Moreover, an overview of the state-of-the-art on nides (TMCs) (MoS2, VS2, NiS2, CoSe,
graphene-based electrode materials and its different composite with transition NiSe, MoSe2, MoTe2, NiCo2S4),[47–73] and
metal oxides, transition metal hydroxides, conducting polymers, transition metal other materials such as MXene,[8,74–78]
chalcogenides, and MXene-based electrode materials for MSCs are discussed and black phosphorus,[79] metal nitrides, rare-
earth oxide/hydroxides,[80–84] and metal–
their electrochemical performances are summarized. Furthermore, this review
organic framework (MOF)[85–87] show a
concludes with perspectives and outlooks. redox reaction mechanism which comes
under pseudocapacitance category.
Generally, these two electrode materials
are merged to form composites or hybrids
1. Introduction electrode materials are exhibiting better electrochemical per-
formance. However, the conventional SCs can be used in
The electrochemical energy storage system is growing rapidly to laptops, cellular phones, and electrical vehicles and girds,
store the energy which has been produced from solar, wind, and whereas the usage of conventional SCs is restricting in micro-
thermal energy.[1–6] The two main electrochemical energy stor- sensors, modern wearable and portable microelectronic
age devices are metal-ion batteries and supercapacitors (SCs) that devices, integrating flexible and wearable on-chip devices,
are used extensively in laptops, iPods, cellular phones, medical and microhealthcare devices with lightweight, low cost,
devices, aerospace, nanorobots, electrical vehicles, and electrical compactness, and flexible.[88–90] Therefore, the need of mini-
grids.[7–12] Even though both devices show a different charge- aturized energy storage devices is attained more demand for
storage mechanism, yet they have similar components such as micro-/nanoscale devices.
a positive and negative electrode, an electrolyte, and a separator. The recent trend toward the miniaturization of energy storage
In the past several decades, SCs have obtained a positive impact devices such as microbatteries (MBs), micro-SCs (MSCs), and
on both industry and academic owing to their excellent power microscaled fuel cells has received more interest among the
density, remarkable cycle life, and better rate performance. research for developing a next-generation small-sized energy
The energy storage mechanism in SCs shows two distinct types storage devices with flexible and lightweight. MBs are available
of electrochemical double-layer capacitor (EDLC) and in commercial markets and used in many miniaturized energy
devices, but suffer from low specific power and poor long-term
Dr. B. Kirubasankar, B. Balan, Prof. S. Angaiah stability, which limited the usage of MBs in various miniaturized
Electro-Materials Research Laboratory, Centre for Nanoscience and devices.[91] MSC is an alternative power source for microsized
Technology
Pondicherry University integrated energy devices and recently both academic and indus-
Pondicherry 605 014, India try start to develop this device.[92] Compared with MBs, MSCs
E-mail: asubramania.nst@ponduni.edu.in show some ultrahigh power density, fast charge/discharge capac-
Dr. B. Kirubasankar, Prof. C. Yan ity, and long cycle life. In both MBs and MSCs, the ion diffusion
School of Materials Science and Engineering length increases with an increase in the mass loading, therefore
Jiangsu University of Science and Technology an optimum mass loading is highly commanded in microelectr-
Zhenjiang 212003, P. R. China
odes.[93,94] The integration of MBs and MSCs exhibiting remark-
The ORCID identification number(s) for the author(s) of this article able energy storage attained a high power delivery rate, high rate
can be found under https://doi.org/10.1002/ente.202000844. capability, and robust cyclability. First, carbon-based MSCs are
DOI: 10.1002/ente.202000844 fabricated in 2006 by two different groups: In et al. made a
Energy Technol. 2021, 2000844 2000844 (1 of 24) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.entechnol.de
SC of 350 350 μm2 electrode area by origami process in 3D determining the performance of a conventional SC.[102,103]
geometry structure; Sung et al. fabricated flexible MSCs of Therefore, MSCs are difficult to compare based on gravimetric
2 2 mm2 by photolithography combined with electropolymeri- capacitance. Because of the on-chip planar configuration, the
zation. Both MSCs exhibit a low areal capacitance.[95,96] After this total mass loading of active electrode material is negligible.
an intense research is started to fabricate the microelectrode for So, the volume and substrate area are more suitable for deter-
MBs and MSCs, to improve the performance of microelectrode mining the MSC performance.
in the aspects of design, structure, fabrication technique, Depending on the thickness of the electrode, the volumetric
mechanical strength, electrochemical stability, rate capability, capacitance can be calculated. In the case of thicker electrodes,
capacitance retention under different current density, tempera- the volumetric capacitance is decreased. The EDLC-based elec-
ture conditions, and so on.[97] The geometrical size and area trode exhibits a complex internal pore structure and inaccessible
of both MBs and MSCs devices can occupy only an area of a mil- redox sites for pseudocapacitor-based electrode. Therefore, the
limeter or centimeter scale and less than 10 μm thickness. areal capacitance, energy, and power densities based on the area
Various configurations for the fabrication of MSC electrodes are the important parameters for MSC. Based on the following
include fibrous electrode used in core–shell configuration, equation, the performance of one microelectrode of MSCs can be
thin-film electrode used in the sandwich configuration, interdi- evaluated:
gital microelectrode used in a planar configuration, and Areal capacitance Cs (F cm2)
patterned/microbuilding blocks electrode used in 3D configura- R
tion. In the present prototype, the planar configuration has more IdV
Cs ¼ ðfrom CVÞ (1)
advantages when compared with other configurations owing to 2aΔV
the substantial electrode–electrolyte contact surface, separator
IΔt
free, shorter ionic diffusion distance, and so on. The 3D config- Cs ¼ ðfrom GCDÞ (2)
uration is a novel and newer idea for the next- aΔV
generation MSCs.
Energy density Es (W h cm2)
Numerous materials are available as an electrode for fabricat-
ing MSCs. Among various electrode materials, 2D graphene- Cs V 2
based electrode materials, isolated from graphite, have been Es ¼ (3)
7200a
providing an outstanding electrochemical performance since
2004. Owing to their remarkable physical, chemical, electrical, Power density Ps (W cm2)
and mechanical properties, the 2D one-atom-thick carbon sheet
has sp2 hybridization with 2630 m2 g1 high surface area, Es
Ps ¼ (4)
15 000 cm2 V1 s1 electron mobility, and 550 F g1 theoretical Δt
capacitance.[98–100] Therefore, for the past few decades, it has
been used in energy storage and conversion applications. The power density can also be calculated from impedance
Even though, in MSC, the usage of graphene as a microelectrode analysis, which is shown in Equation (5)
has been studied extensively due to their unique properties, MSC
ΔV 2
single-layer graphene achieved a maximum theoretical capaci- Ps ¼ (5)
tance of 21 μF cm2.[101] However, the microelectrode made 4aESR
up of 2D graphene for MSC has more advantages such as where ∫ IdV represents the integral areas of the cyclic voltamme-
ultra-thickness, transparency, facile fabrication process, high try (CV) curve, Cs indicates the areal capacitance, a denotes the
conductivity, mechanically stable, flexibility, and miniaturization. total area of a microelectrode, ΔV represents the working poten-
This review fully deals with the recent progress of graphene- tial range, Δt is the time, ESR is equivalent series resistance, Es
based electrodes for MSCs. In this study, the performance of indicates the energy density, and Ps represents the power density.
MSCs is evaluated, and difference between macro-SCs and In the MSCs, microelectrodes are stacked in a series and par-
MSCs, with a focus on the various fabrication techniques for
allel manner to achieve higher areal capacitance, energy, and
MSCs, and the state of the art on graphene and its various com-
power densities. Based on the following equation, the perfor-
posites/hybrids-based electrode materials used so far for MSCs
mance of stacked MSCs can be evaluated:
are highlighted. Finally, the further developments, challenges,
Areal stack capacitance CA (F cm2)
and the outlooks of MSCs are presented in detail.
Cs
CA ¼ (6)
A
2. Performance Evaluation of MSCs
Energy density EA (W h cm2)
In conventional SCs how much power is delivered and how
much energy is stored per unit weight or volume can be calcu- Cs V 2
lated. To assess the electrochemical performance of SCs, their EA ¼ (7)
7200A
specific capacitance, specific energy, and power densities can
be calculated with respect to their active mass loaded (weight From the galvanostatic charge–discharge (GCD) curve, a non-
or volume of the electrode material). Based on the active mass, linear change of voltage is observed; the energy density can be
thickness and density of the electrodes play a crucial role in calculated using the following equation

Z t2 which seems to be a vertical sandwich-type structure as shown

EA ¼ IV t dt (8)
t1 in Figure 1a. However in the case of MSCs, an inter-
digitated on-chip design is used. Therefore, both differ in their
Power density PA (W cm2) structural design as well as diffusion behavior of electrolyte ions.
In MSC, mainly three different kinds of device configuration
IV t
PA ¼ (9) have been used so far: fibers shape, in-plane, and 3D
A configurations.
Energy efficiency η The mass loading of electrodes, the thickness of electrodes,
and separator are the essential parameters for SCs; an appropri-
η¼
E discharge
(10) ate mass loading is in order of 1–10 mg cm2 for electrodes, a
E charge range of 10–100 μm thickness for electrodes, and 25–
30 mm for separators. To improve the electrochemical perfor-
where I represents the average current, V is the voltage range, Cs mance of SCs, the thickness or mass loading of the electrodes
indicates the areal capacitance based on one microelectrode, A is increased under a fixed area which, typically results in higher
denotes the entire geometrical area (i.e., included the entire area ion diffusion length, increase in electronic resistance, and low
of both positive and negative microelectrodes and the interspace
power density. However in the case of MSCs, an interdigitated
between them), Vt is the discharged voltage, Echarge is the charg-
architecture consists of numerous microelectrode arrays in a sin-
ing energy, and Edischarge is the discharging energy.
gle electrode fabricated on a substrate. We represents the width of
the microelectrode, Wg indicates the gap between microelec-
3. Differences between SCs and MSCs trode, L is the entire length of the electrode, and t denotes the
thickness (Figure 1b,c); a typical size of We, Wg, and t is a range
In general, both SCs and MSCs have many differences based on in 10–100 μm and L is a range in mm or cm.[104] In MSCs, ion
their electrode structure, performance, application, and so on. conduction path of the electrolyte is constant; if Wg is high, the
The performance of SCs is normalized by the active mass/vol- diffusion path is increased which leads to high ESR and power
ume of the electrode material, whereas the performance of density drops. Therefore, the ratio of We and Wg is maintained
MSCs is normalized by the active area of the electrode material. under some optimum value to attained high energy and power
The usage of SCs ranges from laptops to electrical grids, but densities with low resistance. The parameters We, Wg, L, and t
MSCs can be specifically used for the micro/nanopower devices. can be tuned by fabrication methods, to achieve better perfor-
Based on the electrode structure, the conventional symmetric mance of MSCs. In summary, the better electrochemical perfor-
and asymmetric SCs (SSCs and ASCs) consist of two electrodes, mance of MSC is primarily dependent on the design aspects and
which are separated by a separator soaked with electrolyte, configuration of an integrated architecture.
Figure 1. Schematic representation of a) conventional sandwich-type SSC and b,c) in-plane MSCs. Reproduced with permission.[104] Copyright 2018,
American Chemical Society.

4. Various Fabrication Techniques for MSCs Inkjet printing is a promising, low-cost, precision over the
microelectrodes, mass productions, without a physical mask
Large-scale fabrication of graphene-based microelectrodes for the and used in a variety of substrates (Figure 3). A digital inkjet
on-chip MSC is an essential step. Up to now, there are various printer is used to print the microelectrode onto a substrate,
techniques available for the fabrication of graphene-based MSC wherein the active material is a conductive ink.[117] In this tech-
(G-MSC). The various fabrication techniques for graphene-based nique, the production of conductive ink is a crucial role. Hersam
MSCs are based on their dimensions, precision, commercializa- et al. formulated highly stable graphene ink using ethyl cellulose
tion, and trend. Here, we summarized the various processing as a stabilizing agent for the inkjet printing process. The pre-
techniques of graphene-based MSCs, as shown in Table 1. pared ink exhibits a viscosity and surface tension of 12 mPa s
Based on the dimension, G-MSC can be classified into 1D (fiber and 33 mN m1 at 30 C, respectively. A Fujifilm Dimatrix
configuration) and 2D and 3D (in-planar configuration), accord- Printer (DMP-2800) is used to print the patterned features on
ing to the fabrication techniques.[105] a substrate with a precision thickness of 20 μm and a line width
of 60 μm.[118]
4.1. Printing Technology R2R gravure printing (roll to roll) is a large-scale process,
which uses flexible substrate and a very fast printing technique
Printing technology is an indirect fabrication technique for the as shown in Figure 4. In this technique, three processes such as
manufacture of large-scale microelectrodes for many microe- doctoring, off, and set are used: first, ink is filled in engraved cell
nergy storage devices. Owing to their inexpensive, minimal wast- and excess is removed by a doctor blade; second, the ink is trans-
age of active material, commercial viability and used in flexible ferred to rubber by applying force; and finally, the process ink is
substrates. In this technique, the printing ink has to be prepared used to print the pattern on the substrate. Recently, Huang et al.
from active materials and printed on a well-established patterned used gravure printing to develop a planar MSC using water-
substrate.[106–110] It can be easily processed in a very large-scale soluble graphene/polyvinylalcohol (PVA)–H3PO4 and obtained
factory production. In the fabrication of G-MSCs, print technol- an areal capacitance of 37.5 mF cm2 (@ 5 mV s1).[119]
ogy is also an important technique.[111,112] In printing technology 3D printing technique has been attracted more recently
itself, different types of printing techniques such as screen print- toward the fabrication of MSCs.[120] This technique develops
ing, ink-jet printing, and R2R printing (roll to roll) have been 3D electrodes for MSCs, which solves numerous disadvantages
used so far for the fabrication of MSCs. associated with 2D printing technique (screen, inkjet printings).
Screen printing is a simple, conventional, low processing However, in 3D MSCs can accommodate more active materials
time, maintained uniform thickness and low-cost technique. within the minimum surface area. Major issues such as surface
The active material ink can be transferred to the desired pattern area scarcity, electrochemical mass transfer kinetic, and migra-
woven mesh and pressed to get a pattern on the substrate by an tion/diffusion of electrolyte ions pathways have been rectified by
ink-blocking stencil (Figure 2). The inks can be prepared from this 3D printing technology. The 3D electrodes are easily fabri-
various nanomaterials such as graphene/PANI,[113] MnO2[114] cated by successive layer deposition using a computer-aided
and so on, and the substrates can be a paper or cloth.[115] For method such as computer-aided design (CAD) and computer-
example, nitrogen-doped reduced graphene oxide (N-rGO) ink aided manufacture (CAM). It offers numerous advantages low-
was prepared by Xie’s group. N-rGO microelectrode was devel- cost, facile, scalable, fast fabrication, and complex architectures.
oped using screen printing technique and fabricated MSC with The 3D printing technologies manifest a multitude of fabrication
an effective area of 0.39 cm2 and 10 mm thickness, delivered a techniques for printing 3D architectures electrodes for MSCs
high areal capacitance of 3.4 mF cm2.[116] such as extrusion printing, aerosol jet printing, fused deposition
Table 1. Overview of various processing techniques of graphene MSCs.
Technique Advantage Disadvantage Dimension Industrialization Trend Precision Cost
Printing Simple Ink processing 2D/3D Large Yes Medium Low

Flexible substrate Coagulation of ink
Continuous production
No wastage of active materials
Laser Multiple dimension pattering High temperature 1D/2D/3D Large Yes High Medium
Direct reduction of GO
No mask
Wet-spin Fibrous graphene Solution processing 1D Medium Limited Low Low
Low temperature Wastage of active materials
Electrodeposition Short time Metallic/Conductive substrate 2D Medium Limited Low Low
Direct reduction of GO Irregular deposition
Simple
Photolithography Ultrafine pattering Photomask 2D Medium Yes High High
Effective fabrication High temperature
More processing time

Figure 2. Schematic representation of fabricated planar-type MSC via screen printing technique. Reproduced with permission.[115] Copyright 2014, IOP
Publisher.
modeling, jet printing, and laser processed printing.[121–123] Song 4.2. Laser Technology
et al. fabricated a 3D rGO electrode in 3 3 array by microextru-
sion method, as shown in Figure 5. The areal and volumetric Laser technology is a direct fabrication technique with high
capacitance of 3D rGO electrode is increased by increasing precision for the fabrication of microenergy storage devices such
the number of layers.[124] as MBs and MSCs and can be easily opted for large-scale
Figure 3. Schematic representation of MSC via digital printing technique. Adapted with permission.[107] Copyright 2015, Royal Society of Chemistry.

Figure 4. Schematic representation of MSC via gravure printing technique. Reproduced with permission.[119] Copyright 2018, Wiley-VCH.
manufacture process on various kind of substrates as shown in processing of G-MSC, and pattern designing of graphene-
Figure 6a–e.[125] There is no need of masking electrode materials based microelectrodes. Ajayan et al. used the laser for both reduc-
to undergo a high-temperature process during fabrication. In the tion of GO and patterned microelectrode of various designs such
microenergy storage device, a major problem is electrical short as a parallel column, concentric circles, and hair-brush-based
circuits; the laser fabrication technique is one of the best solu- MSC (planar configuration) in free-standing GO film.[126] It
tions to overcome the aforementioned problem. This technique has the advantage to form porous rGO due to localized heating
can be easily fabricated microelectrode for G-MSC in high pre- and gas release during the decomposition of functional groups.
cision. The major advantages are area reduction of GO, Similarly, Kaner et al. directly developed more than 100 MSCs
Figure 5. Schematic representation of MSCs via 3D printing technique. Reproduced with permission.[124] Copyright 2017, Royal Society of Chemistry.

Figure 6. a–c) Schematic representation of direct laser-scribed technique on various form of carbon precursor. Reproduced with permission.[125]
Copyright 2018, American Chemical Society. d) Laser-scribed graphene (LSG)-based interdigitated electrode on an organic flexible substrate.
e) Same onto polydimethylsiloxane (PDMS). Reproduced with permission.[128] Copyright 2012, American Chemical Society.
using GO coated on Lightscribe DVD by direct laser writing (i.e., In this fabrication, the microfluidic tube can be used to prepare
laser scribing) in less than 30 min.[127] Laser-induced graphene graphene fibers. The prepared viscous solution is mixed with eth-
(LIG) is a direct photothermal conversion of sp3 carbon to sp2 anol and filled in microfluid tubes to get solidified. To obtain
carbon, which attracted the researchers for the production of MSC electrodes, the microfluid tubes are further reduced and
porous graphene films from the commercially available polymer. dried. The surface morphology and porosity of the fiber are deter-
Graphene-based interdigitated electrode for in-plane MSC can mining the performance of MSC. A direct wet-spinning tech-
easily be fabricated using laser-scribed technique as shown in nique is used by Gao et al. to demonstrate an assembled
Figure 6d,e.[128] In-plane MSC is prepared by Tour’s group using asymmetric fiber-type MSC using MnO2-coated graphene fibers
LIG microelectrodes from polyimide (PI) films and studied their as a positive electrode and graphene-CNTs hybrid fibers as a
electrochemical performance.[129] negative electrode and achieved an areal capacitance of
23.6 mF cm2 in a working potential of 1.6 V.[130] Ye et al.
made graphene fibers by wet-spin coating and flexible
4.3. Wet-Spin Technique MSC fabricated by using PVA/H2SO4 gel electrolyte as shown
in Figure 7. The resulting flexible MSC exhibits a high cycle
1D fibrous graphene electrode materials for MSCs can be synthe- stability of 98.5% (over 10 000 cycles) and an areal density of
sized effectively by wet-spinning technique as shown in Figure 7. 228 mF cm2.[131]

Figure 7. Schematic representation of fabricated fiber-type MSC via the wet-spinning technique. Reproduced with permission.[131] Copyright 2015, Royal
Society of Chemistry.
4.4. Electrodeposition Technique 4.5. Photolithography Technique
Electrochemical deposition of active materials on a metallic sub- Photolithography is another direct fabrication and effective tech-
strate is a direct method for the preparation of microelectrode. nique for the preparation of G-MSC. In this technique, three pro-
This method is a facile technique to prepare graphene compos- cesses such as pattering, deposition and removal are used: first, a
ite/hybrid-based MSC. Electrochemical deposition is used by well patterned photoresist have to develop on the substrate; sec-
Yan’s group to fabricate the symmetric and asymmetric G- ond, metal deposition on the patterned photoresist; and third
MSC. In symmetric MSC, graphene quantum dots are coated etching/removal of remaining photoresist to obtained G-MSC.
in Au substrate and used as both positive and negative electrodes. For the fabrication of hierarchical structured MSC, the photoli-
Similarly, in asymmetric MSC, MnO2 and graphene quantum thography is combined with the ion-etching process (Figure 9).
dots are coated on Au substrate as positive and negative electro- Many research groups are involved in this technique to fabricate
des, respectively.[132] PANI and graphene quantum dots interdi- MSC. Ha et al. prepared multilayered patterned graphene
gital Au electrodes are fabricated by a controllable and simple composited with carbon nanotube (MG/multiwalled carbon
two-step electrodeposition process as shown in Figure 8.[133] nanotubes [MWCNTs]) microelectrode by a photolithography
Recently, a hybrid microelectrode (rGO/Mn3O4) is prepared method. Using that microelectrodes, a solid-state MSC is fabri-
by electrodeposition technique by simultaneous reduction of cated; an areal capacitance of 2.54 mF cm2 is observed.[135]
GO to rGO and assembling rGO/Mn3O4 on the Zn surface.[134] Mullen et al. used photolithography technique to construct a
Figure 8. Schematic representation of fabricated in-plane MSC via electrodeposition technique. Reproduced with permission.[133] Copyright 2017, Royal
Society of Chemistry.

patterned interdigital finger using rGO on Si wafers.[136] area, earth-abundant, controllable porosity, facile processability,
The photolithography technique is combined with some other and inert electrochemistry properties, carbon-based nanostruc-
technique for the fabrication of MSC, which attributes an ture materials are used to fabricate MSC. Among them graphene
improved areal and volumetric capacitance, energy, and power has been used a lot, as discussed later.
density. For example, Chen et al. synthesized suspended wavy In 2011, Ajayan et al. reported ultrathin planar MSC using
graphene microelectrode by a photolithography technique on a single-layer graphene by chemical vapor deposition (CVD)
flexible polymer substrate, to overcome the rigid characteristic method as well as multilayer rGO as microelectrodes. A single-
of interdigital electrodes. Moreover, the MSC shows excellent layer graphene-based MSC exhibits 80 μF cm2, whereas
cycle stability of 96.6% for 10 000 cycles.[137] multilayer rGO-based MSC exhibits around 394 μF cm2.[138]
In a similar passion, microwave plasma CVD method is com-
bined with optical lithography and etching to produce μm-thick
5. Graphene and Its Composites-Based Electrode graphitic petal as microelectrode for MSC. The fabricated G-MSC
is capable of giving an energy and power densities of
Materials for MSCs 9.5 mW h cm3 and 235 W cm3, respectively.[139] Kaner et al.
5.1. Graphene fabricated high-power G-MSC synthesized by laser reduction
of GO films on Lightscribe DVD burner. Sixteen interdigitated
Non-Faradic charge storage mechanism (EDLC behavior) is G-MSCs were constructed by 8 (þve) and 8 (–ve) microelectrodes
observed for all types of carbon-based electrode materials and with PVA/H2SO4 hydrogel electrolyte, which achieved a stack
has been extensively used in energy storage applications. capacitance of 2.35 F cm3 and 200 W cm3 of high power den-
Owing to inexpensive, available in various forms, large surface sity.[127] Chen et al. fabricated stretchable MSC using a wavy
Figure 9. Schematic representation of fabricated planar-type interdigital microelectrodes via photolithography technique. Reproduced with permis-
sion.[136] Copyright 2014, Royal Society of Chemistry.

suspended graphene ribbon which shows a lower sheet resis- 5.1.1. Heterogeneous Graphene
tance (4.5 102 Ω sq1) and excellent energy and power densi-
ties.[137] In 2013, a flexible in-plane rGO–MSC is fabricated by N-rGO is prepared by Xie’s group using screen-printing technol-
photolithography with electrophoretic methods, packed using ogy. The all-solid-state MSC is fabricated; a single MSC exhibits a
gel electrolyte (PVA/H3PO4) which delivered a 462 μF cm2 of potential of 0.8 V and a specific capacitance of 3.4 mF cm2. To
areal capacitance and 98% of high Coulombic efficiency.[140] A improve its specific capacitance and potential window, they made
wire/fiber-type flexible MSC made up of electrochemically four MSC devices which are connected in parallel, connected in
rGO on Cu wire by electrodeposition method, a length series, and connected in combination of parallel and series as
capacitance of 40.5 mF cm2 with a potential wide of 1 V.[141] shown in Figure 11.[116] Ogale et al. reported a planar flexible
Direct laser writing on PI to form graphene polyhedral MSC; carbon microelectrode derived from Mushroom shows
network-based flexible in-plane MSC with LiCl/PVA electrolyte an intense 2D peak, while single-layer graphene also exhibits
demonstrated a high areal capacitance of 34.7 mF cm2 an intense 2D peak. The prepared carbon from Mushroom
(@ 0.1 mA cm2) with a power density of 11 mW cm3.[142] seems to be few-layer graphene and it is confirmed by XRD,
An ultraminiature MSC (100 8 μm2) is produced by Raman, and transmission electron microscopy (TEM) analysis.
direct femtosecond laser writing on GO film to form rGO Using CO2 laser, the microelectrode is fabricated under PVA/
microelectrode with interspacing of 2 μm and 30 pL of H2SO4 as gel electrolyte delivered a capacitance of 9 mF cm2
microelectrolyte is drop-cast on MSCs. This device exhibits a (areal), 12.92 mF cm3 (stack), energy and power densities
capacitance of 6.3 mF cm2 and 105 F cm3 with excellent of 1.8 mW h cm3 (@ 0.05 mA cm2) and 720 mW cm2
cycle stability.[143] Munuera et al. made an in-plane MSC using (@ 1 mA cm2) with excellent cycle stability.[146] To improve
electrochemically exfoliated graphene (EG) (Figure 10), which the electrochemical properties of graphene, some research
exhibits areal capacitance of 0.27 mF cm2, and energy and groups made heteroatoms-doped graphene-based microelectrode
power densities of 0.03 Wh cm2 and 0.003 mW cm2, respec- for MSC. For example, in 2015 Tour et al. synthesized boron-
tively.[144] To achieve high electrical and ionic conductivity doped graphene by a simple laser induction process on PI sheets
between the electrode of graphene films, a nano-GO is used containing boric acid. No morphology change is observed after
as an electrolyte by Li group. They fabricated all-graphene the loading of boron, reassembly like a ridge and wrinkle nano-
MSC by an inkjet printing technique. This device shows sheets like structure. This system shows high areal capacitance of
areal capacitance of 313 μF cm2 and power density of 16.5 mF cm2 (3 times higher than nondoped MSC devices) and
4 mW cm3.[145] 90% retention over 12 000 cycles.[147]
Figure 10. a) Photographs of printed in-plane MSC, b) SEM image substrate, c) SEM image of graphene pattern with PVA/H2SO4 gel electrolyte, elec-
trochemical performance of MSC: d) CV curves, e) GCD curves, and f ) cycle stability test. Reproduced with permission.[144] Copyright 2020, American
Chemical Society.
Figure 11. Electrochemical performance of single MSC and MSC device connected in parallel and series: a,b) CV and GCD curves of four MSC devices
connected in parallel, c,d) CV and GCD curves of four MSC devices connected in series, and e,f ) CV and GCD curves of four MSC services connected in a
combination of series and parallel. Reproduced with permission.[116] Copyright 2014, Royal Society of Chemistry.
Feng et al. developed a high-volumetric planar MSC using tetrafluoroborate [EMIMBF4]) electrolyte. 388.6 m2 g1 surface
sulfur-doped graphene via spray coating followed by thermal area with electrical conductivity of 30785 S m1 is observed for
treatment. Ultrathin microelectrode of 10 nm is coated on a the N-doped graphene possess. The fiber-type gel electrolyte-
wafer, which shows a pseudocapacitive behavior and possesses based MSC device exhibits a high capacitance of
a high capacitance of 582 F cm3 (@ 10 mV s1) with superior 1132 mF cm2 but suffers from energy and power densities,
rate capability, fast response of 0.26 ms, and an ultra-power den- whereas ionic liquid-based MSC delivers an outstanding energy
sity of 1191 W cm3.[148] To know the electrochemical perfor- density of 95.7 μWh cm2 and power density of 15 W cm2.[149]
mance of nitrogen-doped porous graphene fibers via the Recently, Yu et al. synthesized an O, P-functionalized holey gra-
microfluidic method, Chen’s group conducted a comparative phene (FHG) by an electrochemical exfoliation process. An in-
study of fiber-type MSC using aqueous gel (PVA/H3PO4) and plane MSC is fabricated using the synthesized FHG and studied
ionic liquid (PVDF-HFP/1-ethyl-3-methylimidazolium the effect of thickness. The MCS-12 exhibits a high areal and
volumetric capacitance of 6.41 mF cm2 and 30.51 F cm3, under a wide potential window of 3 V and a power density of
respectively, with an energy density of 4.24 mWh cm3. It 135 W cm3.[152] In 2018, a flexible MSC is fabricated using
showed excellent cycling stability of 88.6% even after 10 000 rGO/MWCNT as a microelectrode via the laser-scribed method,
cycles and 99.7% of capacitance retention over 500 bending which shows a remarkable volumetric capacitance of 46.6 F cm3
cycles.[150] Liu et al. made asymmetric heterogeneous gra- and the energy density of 6.47 mW h cm3 (@ 20 mA cm3) and
phene-based MSCs (functionalized oxygen-doped graphene a minimum loss of 12% even after 10 000 cycles (Figure 12).[153]
[FG]||iodine-doped graphene [IG]). Both electrostatic and faradic Crean et al. used functionlized few layer graphene (FLG) and
charge storage mechanisms have been taken place between these MWCNT nanocomposite-based microelectrode fabricated by
microelectrodes. This device can capable of delivering 1.6 V, 83% doctor blading and laser etching technique. An in situ Raman
capacitance retention even after 5000 cycles, 4.75 mWh cm3 microscopy was used to study the charge storage mechanism
energy density, and 61.55 W cm3 power density.[151] and the pseudocapacitive behavior of the microelectrode was
found. The normalized volume and areal specific capacitance
is found to be 19.9 mF cm3 and 19.5 mF cm2, respectively.[154]
5.1.2. Graphene/Other Carbon Composites
To improve the electrochemical properties of graphene nano- 5.1.3. 3D Printed Graphene

sheets, a composite with CNTs has been developed. For example,
Tour et al. synthesized graphene/CNT carpets on Ni substrate for Recently, 3D graphene microelectrodes are used in MSC, and a
MSC. This exhibits a volumetric energy density of 2.42 mW h cm3 schematic representation of ions diffusion and migration in the
in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4) conventional electrode and 3D printed electrode is shown in
Figure 12. a) An optical photo of MSC bent with tweezers demonstrates the flexibility of the microdevice. b) Schematic diagram of assembling an all-
solid-state flexible MSC; electrochemical performance of an assembled MSC using PVA/H3PO4 gel electrolyte, c) CV curves at various scan rates (5–
100 mV s1) with a voltage window of 1.0 V, d) GCD curves at different current densities (20–100 mA cm3), e) the CV curves under different curvatures of
0 , 45 , 90 , 135 , and 180 at a scan rate of 20 mV s1, f ) cycling performance at 50 mA cm3. Inset shows the GCD curves of the first and the last five
cycles. Reproduced with permission.[153] Copyright 2018, Elsevier.
Figure 13.[155] In 2018, Fan et al. proposed a 3D scalable gra- by Alshareef group. This porous graphene possesses
phene aerogel hybrids can capable of delivering a high areal 338.3 m2 g1 excellent surface area and 66.2 S cm1 conductivity.
capacitance of 639.5 mF cm2.[156] Lignin derived 3D graphene The planar MSC device exhibits an aerial capacitance of
microelectrode for planar MSC via laser lithography formed 25.1 mF cm2, and volumetric energy and power densities of
Figure 13. Schematic representation of ion migration in the conventional thick-film electrode and 3D printed G/MWCNT microelectrode. Reproduced
with permission.[156] Copyright 2018, American Chemical Society.
Figure 14. a,b) Photograph of a ternary hybrid composed of rGO–MnO2–Ag nanowires (RGMA) in-plane flexible and transparent MSC onto the PET
substrate. c) Photograph of ionic liquid gel electrolyte. d) Photograph of RGMA-MSC bent with different angles. Electrochemical behaviors of RGMA-
MSC: e) CV curves bent with different angles. f ) Galvanostatic charge/discharge curves at a constant current density of 85 mA cm3. g) Specific capaci-
tance as a function of cycle number. Reproduced with permission.[164] Copyright 2015, American Chemical Society.
1 mW h cm3 and 2 W cm3, respectively.[157] 3D printed hetero- and low electronic and ionic conductivities.[159] A fiber-type MSC
geneous graphene doped with nitrogen/oxygen is fabricated by Li is developed by Liu’s group using intertwined δ-MnO2/holey
group. The nitrogen/oxygen-doped graphene (NOG) printing ink reduced graphene oxide (HrGO) fibrous microelectrode solidi-
exhibits an interconnected porous nanosheet like structure. fied in gel aqueous electrolyte (PVA/H3PO4). This fiber-type
The NOG microelectrode is made by layer by layer printing MSC maintained an areal capacitance of 16.3 mF cm2@
(Fisnar F4200N) with 500 μm width and 130 μm spaces 0.05 mA cm2. A 30 cm length of this MSC can easily light up
between them. An areal energy density of 2.59 μW h cm2 and a light emitting diode (LED) of 3 V and regain its original shape
better cycling stability are offered by this NOG MSCs.[158] after 1 h for 45 bend.[160] Shen et al. developed a hybrid flexible
on-chip MSC integrated with a photodetector. A simple hydro-
5.2. Graphene/TMOs thermal method is used for the preparation of rGO/Fe2O3 nano-
composite and then photolithography and plasma etching are
Nanostructured TMOs always hold a promising charge storage used to form microelectrode. In this study, the Fe2O3 hollow
mechanism (pseudocapacitive behavior). Therefore, TMOs have nanospheres are embedded onto rGO nanosheets. The hybrid
been used in all kinds of energy conversion and storage devices MSC device exhibits poor areal capacitance but robust cycling
over the last decade. The usage of TMOs as microelectrode in stability of 92% (over 32 000 cycles).[161] To improve the working
MSC is mainly due to their unimaginable theoretical capacitance, potential, Yan et al. used ionic liquid gel electrolyte
Figure 15. Folded tandem in-plane β-Ni(OH)2–Ag NW |PVA/KOH| rGO–Ag NW-based MSC pack. a) Digital photography of cathode and anode electro-
des connected by a Ag NW circuit. b) Two tandem of MSC in folding. c) A complete tandem of MSC after adding electrolyte between electrodes.
d) Chargedischarge curves at different current. e) Image of red LED lighted up using folded MSC pack. Reproduced with permission.[171]
Copyright 2018, American Chemical Society.
(1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide modification of composite electrode. MSC shows an areal spe-

[EMIM][NTF2]) for the fabrication of MnO2||GQD-based in-plane cific capacitance of 23.04 mF cm2 high tensile strength (from
asymmetric MSC. The presence of ionic liquid improves the fast- 3% to 315%).[165] In 2018, Misra et al. fabricate two MSC devices:
ion conductivity, high ion diffusion in the ionic liquid matrix, one MSCs by layer-by-layer spray-deposited of MnO2–CNT and
and exhibits an ultrafast frequency response and works in the MnO2–rGO (LMSC); another MSC by mixing the same amount
wide working potential of 2.5 V.[162] Asymmetric MSC is fabri- of MnO2–CNT and MnO2–rGO (RMSC) in H3PO4/PVA. The
cated by Jelinek et al. using a freestanding Au/rGO/MnO2 micro- LMSC provides rapid ions diffusion between the electrode and
electrode prepared by a simple electrodeposition technique.[163] electrolyte interface, better cation intercalation with minimum
The hybrid ternary film is developed with rGO/MnO2/Ag NW charge resistance when compared with RMSC. The LMSC offers
fabricated by a simple vacuum filtration followed by thermal a remarkable areal capacitance of 7.43 mF cm2, and the volu-
reduction to form binder-free microelectrode for in-plane flexible metric capacitance of 32.3 F cm3.[166] In 2020, a highly stretch-
MSC on polyethylene terephthalate (PET) substrate and its elec- able MSC is developed with NiO/Co3O4/LIG ternary film by laser
trochemical properties are shown in Figure 11. Ionic liquid elec- processing on a PI film and this electrode is transferred to bio-
trolyte is used to fabricate MSC device and works in a wide degradable polyurethane. The MSC shows 2.4 mF cm2 of areal
potential window of 2.5 V. The electrochemical performance is capacitance and 77.1% of capacitance retention under 50%
well maintained in all the bend angle (0 , 30 , 60 , and 90 ), strain.[167] Plasma-reduced nitrogen-doped graphene oxide
which indicate the robust flexible of the MSCs device, excellent (PNG)||PNG–MoO2-based asymmetric MSCs is fabricated by
high rate capability, and good long-term cycle life (90.3% even laser technique. The fine nanoparticles of MoO2 are embedded
after 6000 cycles) as shown in Figure 14.[164] A ternary MnO2/ on the nitrogen-doped graphene nanosheets with 8.05% of nitro-
graphene/PEDOT nanocomposite-based microelectrode is sim- gen. A newer PVA-LiCl aqueous gel electrode used in the asym-
ply drawn on kirigami-bridged island substrate by pen lithogra- metric microsupercapacitors (AMSCs) device can exhibit a
phy. Highly porous, microparticles are distributed over graphene working voltage of 1.4 V, 38.1 μW h cm3 and excellent bending
sheets and change in hybridization from sp2 to sp3 due to stability over 180 .[168]
Figure 16. a,b) Digital photograph of 3D printed interdigital electrodes based on G-PANI and planar SC. Electrochemical performance of 3D G-PANI
planar SC: c) CV curves. d) GCD curves. e) Specific capacitances versus different current densities. f ) Cycle stability for 1000 cycles at 50 mA cm2
(inset: photograph of a planar device). Reproduced with permission.[180] Copyright 2018, American Chemical Society.
(Figure 15). This MSC system manifests an areal capacitance

of 8.6 mF cm2 with low areal resistance of 0.066 Ω sq1 and
a tandem paper fold MSC supplies a high voltage of 3 V, which
powers an LED light.[171] In 2018, Shahrokhian et al. used
Ni(OH)2-decorated Ni–Cu film on Cu wire substrate for fiber-
type flexible asymmetric MSC (Ni(OH)2/Ni–Cu||rGO/CF), which
delivered a volumetric energy and power densities as
15.04 mWh cm3 and 588 mW cm3, respectively.[172] Han
et al. fabricated a rGO@CoNi-layered double hydroxide (LDH)
hollow fibers microelectrode via a two-step process using capil-
lary glass tubes for the preparation of rGO and in situ electrode-
position of CoNi-LDH. Hybrid fiber microelectrode-based MSCs
show 8.89 W h cm2 and 0.525 m W cm2 with high bending
durability.[173]
5.4. Graphene/CPs
CP is a pseudocapacitive material combined with graphene to

improve the overall electrochemical performance of MSCs.
Yan et al. developed an asymmetric MSC using graphene quan-
tum dots (GQDs) as the negative and PANI as the positive micro-
electrodes by a simple electrodeposition process on Au substrate
and PVA/H3PO4 as the gel electrolyte, which shows a minimum
Figure 17. a) Schematic representation of mask-assisted continuous cen- areal capacitance of 0.67 mF cm2.[133] A flexible fiber-based sym-
trifugal coating, b) GO/PEDOT:PSS films, and c) rGO/PEDOT:PSS films. metric MSC is prepared by Peng’s group using PEDOT–poly(4-
Reproduced with permission.[181] Copyright 2021, Elsevier. styrenesulfonate) [PSS]/G hollow fibers, which show an electrical
conductivity of 4700 S m1, 304.5 mF cm2 of areal capacitance
(@ 0.08 mA cm2) and maintained the cyclic stability up to 96%
5.3. Graphene/TMHOs (after 10 000 cycles) under bending.[174] PEDOT composite with
conductive graphene flakes-based layer-by-layer assembled
The heterostructure combination of graphene with TMHO microelectrode is used to fabricate in-plane MSC by a simple
exhibits remarkable electrochemical performance due to the syn- pen lithography technique on PET flexible substrate. A three-
ergic effect between the pseudocapacitance and double-layer layer film of G/PEDOT with 20 μm shows a lower sheet resis-
capacitance, which enhances the capacitance, cycle stability, tance of 15 Ω sq1 and better conductivity of 32 s cm1. An
and energy and power densities. In 2015, Alshareef et al. fabri- energy and power densities of 1.5 mW h cm3 and 7.7 F cm3
cated three different microelectrodes such as MnO2/rGO, are obtained from the flexible in-plane MSCs device.[175]
Co(OH)2/rGO and PANI/rGO by a photolithography technique Mullen et al. fabricated a stacked PANI/G nanosheets arrays
on Au-coated substrate. Among them, the MSC is fabricated by of 16 nm thin microelectrode on Au-coated PET substrate and
using Co(OH)2 composite with rGO in PVA/KOH has redox PVA/H2SO4 is used a gel electrolyte. This PANI-G||PANI-G
peaks indicate the conversion of Co(OH)2 to CoOOH during MSCs is delivered an areal and volumetric capacitance of
the oxidation and reduction process. The as-fabricated MSCs 210 mF cm2 and 436 F cm3 (@ 10 mV s1), respectively.[176]
show an areal and volumetric capacitance of 2.7 mF cm2 and In 2016, another research group made a heterostructured verti-
54 F cm3, respectively, with the capacitance retention of 77% cally stacked holey graphene/PANI on an Au-coated substrate to
over 5000 cycles.[169] In 2016, Tour et al. developed an asymmet- enhance the ion mobility across the graphene planes and access
ric in-plane MSC and denoted as LIG-MnO2||LIG-FeOOH in the inner surface of PANI, which leads to superior performance.
PVA/LiCl gel electrolyte. LIG is formed on the PI substrate by This H-G/PANI-based MSC shows an ultrahigh stack capaci-
passing CO2 laser and draws the desired pattern for microelectr- tance of 271.1 F cm3 and an energy density of
odes followed by the selective electrodeposition technique for the 24.1 mW h cm3 with better rate capability.[177] In 2017, the same
formation of MnO2 and FeOOH onto LIG. The asymmetric in- Mullen group used electrochemically EG and mesoporous PANI
plane MSC device demonstrated a wide working potential of to develop an in-plane MSC. The EG is functionalized with non-
1.8 V, 64% of rate capability at 10 mA cm2, and volumetric covalent material (1-pyrenesulfonic acid sodium salt) via π–π
capacitance of 5.4 F cm3 (@ 0.25 mA cm2).[170] interaction to form sulfonyl end group and dispersed with
In addition, Ni(OH)2 is an efficient electrode material that can polystyrene-b-polyetheneoxide to form micromicelles after this
be used in hybrid SCs. In a similar passion, a paper-based in- polymerization of aniline onto micelles and then micelles are
plane asymmetric MSC is fabricated by laser printing technique removed by tetrahydrofuran (THF) to form mesoporous PANI
using β-Ni(OH)2–Ag NW as the cathode, rGO–Ag NW as an on the surface of EG. The in-plane MSCs achieved a volumetric
anode, PVA/KOH as the gel electrolyte, and Ag NW is used capacitance of 75 F cm3 (@ 10 mV s1), high-rate capability of
as an interconnecting electrode to avoid current collector 16% capacitance retention up to 105 mV s1, and an excellent
power density of 600 W cm3 with the energy density of 19.3 mF cm2 of areal-specific capacitance at 20 mV s1, 88.6%
6.67 mWh cm3 outperformed lithium-thin film MBs and alumi- capacitance retention over 5000 cycles, and 87.1% capacitance
num electrolytic capacitors.[178] Laser-reduced graphene oxide retention under 50% stretching of MSC device.[184]
(LrGO)@PANI-based in-plane MSC is fabricated on PET sub- To improve the overall performance of the microelectrode, the
strate; here, the laser irradiation is used to the reduction of CPs can be composite with a metal oxide or another polymer.
GO and growth of CP simultaneously. MSC delivers Selvan et al. prepared flexible fibrous MSC using a CoFe2O4/
72 mF cm2 of areal capacitance with 93.5% capacitance reten- rGO/PANI composite fiber as a negative electrode, β-Co(OH)2
tion even after 1000 cycles.[179] In 2018, Bai et al. developed as a positive electrode, and gel PVA–KOH as electrolyte. The pres-
a 3D architecture planar SC by a direct ink writing of ence of β-Co(OH)2, PANI, and CoFe2O4 exhibits redox reaction,
PANI/rGO composite. This novel 3D planar device delivered a which delivers length capacitance of 1.4 F m1 and an energy den-
high areal capacitance of 1329 mF cm2 in H2SO4/PVA gel sity of 2.7 μWh cm1.[185] Wu et al. synthesized an ultrathin mes-
electrolyte; the better electrochemical performance indicates oporous PPy/rGO anchored with polyoxometalate by a template
the synergistic effect of PANI/rGO[180] (Figure 16). method and fabricated in-plane MSC by layer-by-layer deposition
Recently, scalable and fast planar integrated MSC is fabricated followed by mask-assisted etching. PPy/rGO/polyoxometalate
using rGO/PEDOT:PSS by a simple, low-cost technique by Wu (POM)-based MSC manifests an outstanding volumetric capaci-
group. The planer MSC is fabricated by mask-assisted continu- tance of 137 F cm3, the areal capacitance of 115 mF cm2, and
ous centrifugal coating on PET substrate with metal-free current 4% loss of capacitance retention at 180 bending.[186]
collectors as shown in Figure 17. This device delivered a high
volumetric capacitance of 31.8 F cm3 and energy density of
2.8 mWh cm3.[181] This mask-assisted technique is widely used 5.5. Graphene/TMCs
for processing the graphene-free MSCs.[182,183] Yan group made
a 3D porous PEDOT:PSS/graphene sponge to enhance the mechan- 2D TMCs are layered materials shows some unusual physico-
ical flexibility and electrochemical performance of MSC. It exhibits a chemical and electrochemical properties.[187] Their single or thin
Figure 18. a) Schematic representation of a flexible in-plane rGO–CNC||rGO–MoS2MSC. b,c) Digital photographs of the MSC under twisting and bend-
ing. d) LED glow using MSC. Electrochemical behaviors of flexible in-plane rGO–CNC||rGO–MoS2 MSC: e) CVs curves at different potential windows at a
scan rate of 2 V s1. f ) CVs at various scan rates in the optimum potential range of 01.3 V. g) Specific and stack capacitances versus scan rate. h) Long-
term cycle stability under twisting and bending. Reproduced with permission.[104] Copyright 2018, American Chemical Society.
layers provide an enormous surface area, good structural integ- nanosheets due to laser treatment. The electrochemical perfor-
rity, electrochemical activity edge sites, variable oxidation states, mance of 3D LSG/CoNi2S4||LSG using alkaline gel electrolyte
and electrical conductivities, which allow both Faradic and non- (PVA/KOH)-based MSC is studied; the presence of Co and Ni
Faradic charge storage mechanisms. Based on these numerous ions manifests better Faradic redox reaction and operates at a
advantage, this material is also used as a microelectrode in wider potential window of 1.7 V, 49 Wh L1 of energy density
energy storage devices (MBs and MSCs). which is comparable with MBs.[189] An interdigitated coplanar
Zhu et al. reported a bioinspired graphene-based microfiber 3D MSCs is fabricated using the amorphous structure of
for the fabrication of in-plane flexible MSC. Highly oriented gra- NiMoS4–rGO. The porous NiMoS4 nanoparticles are grown
phene microfibers produce from the spider’s spinneret and it can on the rGO surface for promoting ion diffusion. An ionic liquid
act as a microfluidic chip. These microelectrodes show an ultra- electrode is used in this coplanar 3D MSCs, which shows excel-
high electrical conductivity due to the presence of MoS2 lent long-term stability of 94.06% capacitance retention over 7000
(3.12 104 S m1 for rGOcellulose nanocrystal (CNC) and cycles.[190]
3.27 104 S m1 for rGO MoS2). The rGO–CNC and
rGO–MoS2 are used as electrodes and PVA/H3PO4 is used as
a gel electrolyte to assemble the flexible MSC and achieved a 5.6. Graphene/MXenes
working potential of 1.5 V with high energy and power densi-
ties[104] (Figure 18). 2D-MoS2 is an efficient pseudocapacitance Recently, an emerging class of 2D-transition metal carbides and
material, which is incorporated with rGO NS into MWCNT fiber nitrides (MXenes) has been widely used in a variety of energy
microelectrode (MoS2–rGO/MWCNT) and obtained a maximum storage applications.[191] Gao et al. fabricate a 3D MSCs-based
capacitance of 4.8 F cm3 for 6.3 wt% MoS2. An asymmetric flex- (Ti3C2Tx) MXene-rGO aerogel electrode to mainly resist the
ible MSC is fabricated using MoS2–rGO/MWCNT|PVA–H2SO4| degree of oxidation of MXene. This aerogel exhibits a lamellar
rGO/MWCNT, which operates under a high working potential structure with an average thickness of 1.52 nm and also
of 1.4 V and delivers a 5.2 F cm3 with high Columbic restrain 70% from its original volume after the load is released.
efficiency.[188] Moreover, this Mxene-rGO aerogel is packed in a polyurethane
Double TMCs (CoNi2S4, CoNiSe2, etc.) manifest superior elec- (PU) belt for the self-healing process. The laser beam is used to
trochemical properties compared with single TMCs (NiSe2, construct the MXene-rGO MSC in PVA/H2SO4 gel electrolyte
MoSe2). In 2016, Shamsi et al. used CoNi2S4 and LSG as an inter- and packed in a self-healing polyurethane, which exhibits
digitated microelectrode fabricated by direct laser reduction as 34.6 mF cm2 of areal capacitance and loss of 9% over 15 000
well as selective electrodeposition to form a flexible asymmetric cycles as shown in Figure 19. This 3D MSC prototype is cut into
MSC. The LSG/CoNi2S4 microelectrode exhibits a rough nano- two pieces, after 3 min due to self-healing properties. The MSC
sheets-like morphology, whereas LSG shows slight rough rejoined under a pressure and maintained 81.7% of capacitance
Figure 19. Electrochemical properties of MXene-rGO composite-based in-plane self-healable MSCs: a) CV curves at different scan rates range from 1 to
100 mV s1. b) GCD curves at different current densities range from 0.2 to 0.6 mA cm2. c) Area capacitances versus scan rate. d) Cycling stability (@
2 mA cm2) (inset: GCD curve from the 14 990th to the 15 000th cycles). Reproduced with permission.[192] Copyright 2018, American Chemical Society.
Table 2. Summary of the performance of graphene based electrode materials for MSCs.
MSC Electrolyte Configuration W.V. [V] CA CV E.D. P.D. Cycle stability Ref.
[mF cm2] [F cm3] [mW h cm3] [W cm3] (number of cycles)
1–2-layer graphene PVA/H3PO4 Parallel plate 0–1.0 0.08 – 2.8 106a) 2 106b) – 138
6a) 6b)
rGO film PVA/H3PO4 Parallel plate 0–1.0 0.394 – 14 10 9 10 100% (1500) 138
Graphitic petal 1 M H2SO4 Interdigitated 0–1.0 108 270 9.5 292.3 95% (2000) 139
LSG PVA–H2SO4 Interdigitated 0–1.0 2.32 3.05 – 200 96% (10 000) 127
LSG FS/[BMIM][NTf2] Interdigitated 0–2.5 – 2.35 2.1 141 100% (30 000) 127
Graphene microribbons PVA/H3PO4 Interdigitated 0–0.8 0.58 – 0.52a) 0.417b) 92% (5000) 137
rGO PVA/H3PO4 Interdigitated 0–0.8 0.462 359 31.9 324 98% (1000) 140
3D rGO PVA/H3PO4 Parallel wire 0–1.0 283.5 – 0.0393a) 0.0176b) 94.5% (5000) 141
Laser writing of graphene PVA/LiCl Interdigitated 0–1.0 34.7 10.21 1 0.011 80% (3000) 142
Laser writing of graphene PVA/H3PO4 Interdigitated 0–0.5 6.3 105 – – 100% (1000) 143
Graphene aerogels PVA/H2SO4 Interdigitated 0–1.0 0.27 8.5 1.2 0.1 75% (5000) 144
Inkjet printed graphene Nano-GO Interdigitated 0–1.0 0.313 – 0.24 4.33 103 65% (11 000) 145
N-doped rGO PVA/H2SO4 Interdigitated 0–0.8 3.4 – 0.3 0.2 98.4% (2000) 116
B-doped graphene PVA/H2SO4 Interdigitated 0–1.0 16.5 6.6 0.74 – 90% (12 000) 147
S-doped graphene PVA/H2SO4 Interdigitated 0–1.0 – 8.1 3.1 1191 95% (10 000) 148
rGO||iodine-doped graphene PVA/Na2SO4 Interdigitated 0–1.6 8.68 13.37 4.75 61.55 83% (5000) 151
N- and O-doped graphene PVA/H3PO4 Interdigitated 0–1.0 18.70 3.41 0.47 0.01 93% (10000) 158
N-doped rGO PVA/H2SO4 Parallel fiber 0–0.8 1132 – – – 97.1% (10 000) 149
N-doped rGO PVDF-HFP/EMIMBF4 Parallel fiber 0–3.0 306.3 – 0.0957a) 1.5b) – 149
O, P-functionalized HG PVA/H2SO4 Interdigitated 0–1.0 6.41 30.51 4.24 3.96 88.6% (10 000) 150
Graphene/CNT 1 M Na2SO4 Interdigitated 0–1.0 2.16 – 0.16 115 – 152
Graphene/CNT 1 M BMIM-BF4 Interdigitated 0–3.0 3.93 – 2.42 135 98.4% (8000) 152
rGO/MWCNT PVA/H3PO4 Interdigitated 0–1.0 – 46.6 6.47 0.01 98% (10 000) 153
Graphene/MWCNT PVA/H3PO4 Interdigitated 0–1.0 19.5 19.9 – – 80% (10000) 154
3D printed graphene aerogel 6 M KOH Parallel plate 0–0.8 640 3.2 0.053a) 1.545 103b) 90% (10 000) 156
3D LSG PVA/H2SO4 Interdigitated 0–1.0 25.1 6.27 1 2 99.2% (12 000) 157
δ-MnO2/HrGO PVA/H3PO4 Twisted 0–0.8 16.7 – – – 80% (1000) 160
rGO/Fe2O3 PVA/KOH Interdigitated 0–1.0 0.347 11.57 1.61 9.82 92% (32 000) 161
Au/rGO/MnO2 PVA/LiCl Parallel plate 0–0.8 1532 – 0.136a) 0.0958b) 83% (2000) 163
rGO/MnO2/Ag NW Fumed silica/BMIM TFSI Interdigitated 0–2.0 – 4.42 2.3 0.162 90.3% (6000) 164
MnO2–rGO PVA/H3PO4 Interdigitated 0–0.8 7.43 32.3 2.87 – 98.9 % (5000) 166
N-doped rGO/MoO2 PVA/LiCl Interdigitated 0–1.4 33.6 152.9 38.7 0.8 88% (10000) 168
NiO/Co3O4/LIG PVA/H3PO4 Interdigitated 0–0.8 29.5 – – – 99.1% (10 000) 167
Co(OH)2/rGO PVA/KOH Interdigitated 0–0.5 6 119 6 0.390 77% (5000) 169
rGO/CoNi–LDH PVA/KOH Parallel fiber 0–0.6 570 – 8.89 103a) 5.25 104b) 95.3% (2000) 173
LIG–MnO2||LIG–FeOOH PVA/LiCl Interdigitated 0–1.8 21.9 5.4 2.4 2.891 84% (2000) 170
Ni(OH)2/Ni–Cu||rGO/CF 1 M NaOH Parallel fiber 0–1.6 12.2 1220.8 15.04 588 95.7% (5000) 172
6b)
rGO/PEDOT:PSS PVA/H3PO4 Parallel fiber 0–0.8 304.5 143.3 0.0271 a)
66.5 10 96% (10 000) 174
Graphene/PEDOT PVA/H3PO4 Interdigitated 0–1.2 15.3 7.7 1.5 141 81% (2500) 175
Graphene/PANI PVA/H2SO4 Interdigitated 0–1.0 365 760 46 6.353 86.6% (5000) 176
3D PEDOT:PSS/graphene PVA/H2SO4 Interdigitated 0–0.8 19.3 – 1.07 103a) 4 104b) 88.6% (5000) 184
mPPy@rGO-POM PVA/H2SO4 Interdigitated 0–1.0 115 137 4.8 0.645 80% (2000) 186
MnO2/graphen/PEDOT PVA/H2SO4 Interdigitated 0–1.2 23.04 – 41.48 540 90% (2500) 165
rGO–C||rGO–MoS2 PVA/H3PO4 Parallel microfiber 0–1.3 N/A 40 100 102 97% (10000) 104
MoS2–rGO||rGO–MWCNT PVA/H2SO4 Parallel 0–1.4 N/A 5.2 18.3 10 N/A 188
LSG/CoNi2S4||LSG PVA/KOH Interdigitated 0–1.7 N/A 122.4 49c) 0.8d) 93.9% (10000) 189
Table 2. Continued.
MSC Electrolyte Configuration W.V. [V] CA CV E.D. P.D. Cycle stability Ref.
[mF cm2] [F cm3] [mW h cm3] [W cm3] (number of cycles)
GO/Ti3C2Tx PVA/H2SO4 Parallel 0–0.6 34.6 N/A 2.18 0.06 91% (15000) 192
Ti3C2Tx||rGO PVA/H2SO4 Sandwich 0–1.0 2.4 80 0.26 0.06 97% (1000) 193
– – – – – – – – 194
Ti3C2Tx/EG EMIMBF4 Interdigitated 0–3.0 11.2 35 43.7 14.06 100% (10000) –
mWh cm2;
a) b)
W cm2; c)W h L3; d)
W L3; W.V. working voltage; CA, areal capacitance; CV, volumetric capacitance; E.D. energy density; P.D. power density.
retention after the fifth healing.[192] Gogotsi et al. developed a an effective method to achieve high energy and power densities.
flexible asymmetric MSC composed of Ti3C2Tx (titanium carbide Moreover, the G-MSC is also integrating with the energy conver-
MXene) as a negative electrode and rGO as the positive electrode sion PV model and strain sensors. Some reports address the inte-
in gel electrolyte (PVA/H2SO4) on PET substrate. The rGO|| grated on-chip devices, flexible devices, self-healing devices, and
MXene-based MSC indicates a better ion/electrode exchange real-world application of G-MSC. But still, the research is in the
between microelectrodes, working at a potential window of infant stage for this design and patterns for the 3D architecture-
1 V, and delivers the energy and power densities of based G-MSC, which will be a huge interest in next-generation
8.6 mW h cm3 and 0.2 W cm3, respectively.[193] Bao et al. fab- energy storage devices.
ricated an ion gel-based MSCs with MXene and graphene by a The following outlooks need to be addressed for better perfor-
mask-assisted deposition process. Here, the ionic liquid is used mance and real applications of G-MSC: issues in the G-MSC
for preintercalating the MXene films as well as the electrolyte. such as micropacking, substrate, and current collectors have
The resulting EMIMBF4 ionogel-based MSCs represented high to be improved and real 3D G-MSCs with high energy density,
areal energy density of 13.9 μWh cm2 and volumetric energy long-term stability, and flexibility need to be fabricated. Real
density of 43.7 mWh cm3 with 100% cycle stability even after application of G-MSC has to integrate with microenergy storage
10 000 cycles.[194] devices and bio-on-chip devices are scarce.
6. Conclusion and Outlooks Acknowledgements

A.S. gratefully acknowledges the Council of Scientific and Industrial
Graphene-based MSCs are promising energy storage devices for Research (CSIR), New Delhi (Ref. No. 01(2810)14/EMR-II, dt. 26/04/
many microsensors, and wearable and portable microelectronics. 2017) and UGC-BSR-Mid Career Award (No. F.19-214/2018/BSR) for their
The 2D graphene electrode manifests numerous advantages financial support. The authors also gratefully acknowledge the funding of
the National Natural Science Foundations of China (grant no. 51873083)
such as flexibility, mechanical stability, conductivity, facile proc-
and the Postgraduate Research & Practice Innovation Program of Jiangsu
essing, high areal and volumetric capacitance, and long cycle Province (grant nos. SJCX18_0759 and SJCX19_0584).
stability. This review briefly discussed the current trends in
the fabrication technique of G-MSCs, various designs for
G-MSCs, graphene and its composite/hybrids-based microelectr- Conflict of Interest
odes, and the integration of interdigital on-chip devices.
The authors declare no conflict of interest.
However, numerous fabrication techniques are available for
the fabrication of graphene-based MSCs which are still in the
developing stage, and need more insights and optimization over
fabrication. 2D-graphene and its composites/hybrids with car- Keywords
bon, metal oxides, metal hydroxides, CPs, TMCs, and MXene composite electrodes, energy storage, fabrication techniques, graphene,
have been studied extensively apart from the design pattern of microsupercapacitors
microelectrodes, electrochemical performance of MSCs, and
are briefly summarized in Table 2. Already great achievements Received: September 25, 2020
are made by some existing materials for MSCs, but there are still Revised: January 28, 2021
Published online:
many drawbacks in energy and power densities and long-term
stability. Another major threat is using an aqueous gel electrolyte
that is limited to the working potential of G-MSC. To avoid these
[1] P. Simon, Y. Gogotsi, Nat. Mater. 2008, 7, 845.
issues, solid electrolyte, polymer electrolyte, and ionic–liquid [2] L. L. Zhang, X. S. Zhao, Chem. Soc. Rev. 2009, 38, 2520.
electrolyte can be used in G-MSC for better working potential. [3] K. Naoi, Fuel Cells 2010, 10, 825.
Even though the performance of G-MSC has been improved [4] A. S. Arico, P. Bruce, B. Scrosati, J.-M. Tarascon, W. Van Schalkwijk,
in terms of composites/hybrids materials, suitable selection Mater. Sustainable Energy 2010, 4, 148.
of electrolytes and optimized design of microelectrode. [5] R. Liu, J. Duay, S. B. Lee, Chem. Commun. 2011, 47, 1384.
Furthermore, the G-MSC is combined with MBs that will be [6] G. Wang, L. Zhang, J. Zhang, Chem. Soc. Rev. 2012, 41, 797.
[7] A. Borenstein, O. Hanna, R. Attias, S. Luski, T. Brousse, D. Aurbach, [44] W. Sun, Z. Mo, Mater. Sci. Eng., B 2013, 178, 527.
J. Mater. Chem. A 2017, 5, 12653. [45] R. Liu, S. Il Cho, S. B. Lee, Nanotechnology 2008, 19, 215710.
[8] C. Tan, X. Cao, X. J. Wu, Q. He, J. Yang, X. Zhang, J. Chen, W. Zhao, [46] Y.-G. Wang, H.-Q. Li, Y.-Y. Xia, Adv. Mater. 2006, 18, 2619.
S. Han, G. H. Nam, M. Sindoro, H. Zhang, Chem. Rev. 2017, 117, [47] B. Hu, X. Qin, A. M. Asiri, K. A. Alamry, A. O. Al-Youbi, X. Sun,
6225. Electrochim. Acta 2013, 100, 24.
[9] Z. Yu, L. Tetard, L. Zhai, J. Thomas, Energy Environ. Sci. 2015, 8, 702. [48] K.-J. Huang, L. Wang, Y.-J. Liu, Y.-M. Liu, H.-B. Wang, T. Gan,
[10] D. P. Dubal, O. Ayyad, V. Ruiz, P. Gómez-Romero, Chem. Soc. Rev. L.-L. Wang, Int. J. Hydrogen Energy 2013, 38, 14027.
2015, 44, 1777. [49] W. Qiu, J. Xia, S. He, H. Xu, H. Zhong, L. Chen, Electrochim. Acta
[11] G. Xiong, C. Meng, R. G. Reifenberger, P. P. Irazoqui, T. S. Fisher, 2014, 117, 145.
Electroanalysis 2014, 26, 30. [50] J. Feng, X. Sun, C. Wu, L. Peng, C. Lin, S. Hu, J. Yang, J. Am. Ceram.
[12] W. Gu, G. Yushin, Wiley Interdiscip. Rev. Energy Environ. 2014, 3, 424. Soc. 2011, 133, 17832.
[13] S. Chen, W. Xing, J. Duan, X. Hu, S. Z. Qiao, J. Mater. Chem. A 2013, [51] G. Wang, J. Zhang, S. Kuang, S. Liu, S. Zhuo, J. Power Sources 2014,
1, 2941. 269, 473.
[14] M. Zhi, C. Xiang, J. Li, M. Li, N. Wu, Nanoscale 2013, 5, 72. [52] A. Banerjee, S. Bhatnagar, K. K. Upadhyay, P. Yadav, S. Ogale, ACS
[15] H. Jiang, P. S. Lee, C. Li, Energy Environ. Sci. 2013, 6, 41. Appl. Mater. Interfaces 2014, 6, 18844.
[16] Y. H. Li, S. Y. Zhang, Q. M. Yu, Adv. Mater. Res. 2013, 750–752, [53] Z. Wang, X. Li, Y. Yang, Y. Cui, H. Pan, Z. Wang, B. Chen, G. Qian,
894. J. Mater. Chem. A 2014, 2, 7912.
[17] V. Augustyn, P. Simon, B. Dunn, Energy Environ. Sci. 2014, 7, 1597. [54] C. Zhang, H. Yin, Z. Dai, H. Pang, Y. Zheng, Y.-Q. Lan, J. Bao, J. Zhu,
[18] J. P. Zheng, J. Electrochem. Soc. 1997, 144, 2026. ACS Nano 2014, 8, 3761.
[19] M. E. Plonska-Brzezinska, L. Echegoyen, J. Mater. Chem. A 2013, 1, [55] L. Shen, L. Yu, H. Bin Wu, X.-Y. Yu, X. Zhang, X. W. (David) Lou, Nat.
13703. Commun. 2015, 6, 6694.
[20] Y. Bin Tan, J. M. Lee, J. Mater. Chem. A 2013, 1, 14814. [56] S. K. Balasingam, J. S. Lee, Y. Jun, Dalton Trans. 2015, 44, 15491.
[21] H. Xia, Y. Shirley Meng, G. Yuan, C. Cui, L. Lu, Electrochem. Solid-State [57] K.-J. Huang, J.-Z. Zhang, J.-L. Cai, Electrochim. Acta 2015, 180, 770.
Lett. 2012, 15, A60. [58] X. Chia, A. Y. S. Eng, A. Ambrosi, S. M. Tan, M. Pumera, Chem. Rev.
[22] T. Brousse, P.-L. Taberna, O. Crosnier, R. Dugas, P. Guillemet, 2015, 115, 11941.
Y. Scudeller, Y. Zhou, F. Favier, D. Bélanger, P. Simon, J. Power [59] Z. Wu, X. Pu, Y. Ji, M. Jing, Q. Chen, F. Jiao, Electrochim. Acta 2015,
Sources 2007, 173, 633. 174, 238.
[23] W. Wei, X. Cui, W. Chen, D. G. Ivey, Chem. Soc. Rev. 2011, 40, 1697. [60] J. Shi, X. Li, G. He, L. Zhang, M. Li, J. Mater. Chem. A 2015, 3, 20619.
[24] Y. F. Yuan, X. H. Xia, J. B. Wu, X. H. Huang, Y. B. Pei, J. L. Yang, [61] C. Tang, Z. Pu, Q. Liu, A. M. Asiri, X. Sun, Y. Luo, Y. He,
S. Y. Guo, Electrochem. Commun. 2011, 13, 1123. ChemElectroChem 2015, 2, 1903.
[25] L. Cui, J. Li, X.-G. Zhang, J. Appl. Electrochem. 2009, 39, 1871. [62] B. Kirubasankar, S. Vijayan, S. Angaiah, Sustainable Energy Fuels 2019,
[26] M. Kumar, A. Subramania, K. Balakrishnan, Electrochim. Acta 2014, 3, 467.
149, 152. [63] B. Ye, M. Huang, Q. Bao, S. Jiang, J. Ge, H. Zhao, L. Fan, J. Lin, J. Wu,
[27] H. Jiang, J. Ma, C. Li, Chem. Commun. 2012, 48, 4465. ChemElectroChem 2018, 5, 507.
[28] J.-H. Zhong, A.-L. Wang, G.-R. Li, J.-W. Wang, Y.-N. Ou, Y.-X. Tong, [64] B. Kirubasankar, P. Palanisamy, S. Arunachalam, V. Murugadoss,
J. Mater. Chem. 2012, 22, 5656. S. Angaiah, Chem. Eng. J. 2019, 355, 881.
[29] L. Wang, X. Li, T. Guo, X. Yan, B. K. Tay, Int. J. Hydrogen Energy 2014, [65] H. Peng, C. Wei, K. Wang, T. Meng, Z. Lei, X. Gong, ACS Appl. Mater.
39, 7876. Interfaces 2017, 9, 17067.
[30] H. Wang, Z. Xu, H. Yi, H. Wei, Z. Guo, X. Wang, Nano Energy 2014, 7, [66] B. Kirubasankar, V. Murugadoss, S. Angaiah, RSC Adv. 2017, 7, 5853.
86. [67] J. Yang, Y. Yuan, W. Wang, H. Tang, Z. Ye, J. Lu, J. Power Sources 2017,
[31] R. R. Salunkhe, J. Lin, V. Malgras, S. X. Dou, J. H. Kim, Y. Yamauchi, 340, 6.
Nano Energy 2015, 11, 211. [68] B. Kirubasankar, V. Murugadoss, J. Lin, T. Ding, M. Dong, H. Liu,
[32] S. Bag, C. R. Raj, J. Mater. Chem. A 2016, 4, 587. J. Zhang, T. Li, N. Wang, Z. Guo, S. Angaiah, Nanoscale 2018, 10,
[33] V. D. Nithya, N. S. Arul, J. Power Sources 2016, 327, 297. 20414.
[34] R. Wang, C. Xu, J. M. Lee, Nano Energy 2016, 19, 210. [69] L. Hou, Y. Shi, C. Wu, Y. Zhang, Y. Ma, X. Sun, J. Sun, X. Zhang,
[35] Y. Liu, X. Miao, J. Fang, X. Zhang, S. Chen, W. Li, W. Feng, Y. Chen, C. Yuan, Adv. Funct. Mater. 2018, 1705921, 1.
W. Wang, Y. Zhang, ACS Appl. Mater. Interfaces 2016, 8, 5251. [70] L. Ma, L. Xu, X. Zhou, X. Xu, L. Zhang, RSC Adv. 2016, 6, 91621.
[36] T. Nguyen, M. Boudard, M. J. Carmezim, M. F. Montemor, Sci. Rep. [71] P. Xu, W. Zeng, S. Luo, C. Ling, J. Xiao, A. Zhou, Y. Sun, K. Liao,
2017, 7, 1. Electrochim. Acta 2017, 241, 41.
[37] Y. Wang, X. Zhang, X. Li, Y. Liu, X. Wang, X. Liu, J. Xu, Y. Li, Y. Liu, [72] K. Guo, F. Yang, S. Cui, W. Chen, L. Mi, RSC Adv. 2016, 6, 46523.
H. Wei, P. Jiang, M. Liang, RSC Adv. 2017, 7, 50358. [73] S. K. Balasingam, J. S. Lee, Y. Jun, Dalton Trans. 2016, 45, 9646.
[38] L. Wu, L. Hao, B. Pang, G. Wang, Y. Zhang, X. Li, J. Mater. Chem. A [74] Q. Jiang, N. Kurra, M. Alhabeb, Y. Gogotsi, H. N. Alshareef, Adv.
2017, 5, 4629. Energy Mater. 2018, 1703043, 1703043.
[39] M. Moussa, M. F. El-Kady, H. Wang, A. Michimore, Q. Zhou, J. Xu, [75] M. Cao, F. Wang, L. Wang, W. Wu, W. Lv, J. Zhu, J. Electrochem. Soc.
P. Majeswki, J. Ma, Nanotechnology 2015, 26, 75702. 2017, 164, A3933.
[40] K. Balakrishnan, M. Kumar, A. Subramania, Adv. Mater. Res. 2014, [76] V. M. Hong Ng, H. Huang, K. Zhou, P. S. Lee, W. Que, J. Z. Xu,
938, 151. L. B. Kong, J. Mater. Chem. A 2017, 5, 3039.
[41] S. B. Kulkarni, U. M. Patil, I. Shackery, J. S. Sohn, S. Lee, B. Park, [77] Y. Wang, H. Dou, J. Wang, B. Ding, Y. Xu, Z. Chang, X. Hao, J. Power
S. Jun, J. Mater. Chem. A 2014, 2, 4989. Sources 2016, 327, 221.
[42] I. E. Rauda, V. Augustyn, B. Dunn, S. H. Tolbert, Acc. Chem. Res. 2013, [78] M. Narayanasamy, B. Kirubasankar, M. Shi, S. Velayutham, B. Wang,
46, 1113. S. Angaiah, C. Yan, Chem. Commun. 2020, 56, 6412.
[43] J. Han, Y. Dou, J. Zhao, M. Wei, D. G. Evans, X. Duan, Small 2013, 9, [79] M. Akhtar, G. Anderson, R. Zhao, A. Alruqi, J. E. Mroczkowska,
98. G. Sumanasekera, J. B. Jasinski, npj 2D Mater. Appl. 2017, 1, 5.
[80] M. Majumder, R. B. Choudhary, A. K. Thakur, I. Karbhal, RSC Adv. [114] S. Wang, N. Liu, C. Yang, W. Liu, J. Su, L. Li, C. Yang, Y. Gao, RSC
2017, 7, 20037. Adv. 2015, 5, 85799.
[81] S. Arunachalam, B. Kirubasankar, E. Rajagounder Nagarajan, [115] Y. Wang, Y. Shi, C. X. Zhao, J. I. Wong, X. W. Sun, H. Y. Yang,
D. Vellasamy, S. Angaiah, ChemistrySelect 2018, 3, 12719. Nanotechnology 2014, 25, 94010.
[82] S. Arunachalam, B. Kirubasankar, V. Murugadoss, D. Vellasamy, [116] S. Liu, J. Xie, H. Li, Y. Wang, H. Y. Yang, T. Zhu, S. Zhang, G. Cao,
S. Angaiah, New J. Chem. 2018, 42, 2923. X. Zhao, J. Mater. Chem. A 2014, 2, 18125.
[83] S. Vijayan, B. Kirubasankar, P. Pazhamalai, S. Angaiah, [117] M. H. Ervin, L. T. Le, W. Y. Lee, Electrochim. Acta 2014, 147, 610.
ChemElectroChem 2017, 4, 2059. [118] E. B. Secor, P. L. Prabhumirashi, K. Puntambekar, M. L. Geier,
[84] A. Subasri, K. Balakrishnan, E. R. Nagarajan, V. Devadoss, M. C. Hersam, J. Phys. Chem. Lett. 2013, 4, 1347.
A. Subramania, Electrochim. Acta 2018, 281, 329. [119] Q. Chang, L. Li, L. Sai, W. Shi, L. Huang, Adv. Electron. Mater. 2018,
[85] Y. Wang, Y. Liu, C. Wang, H. Liu, J. Zhang, J. Lin, J. Fan, T. Ding, 4, 1800059.
J. E. Ryu, Z. Guo, Eng. Sci. 2020, 9, 50. [120] S. H. Park, G. Goodall, W. S. Kim, Mater. Des. 2020, 193, 108797.
[86] L. Yue, X. Wang, T. Sun, H. Liu, Q. Li, N. Wu, H. Guo, W. Yang, [121] C. Zhu, T. Liu, F. Qian, T. Y.-J. Han, E. B. Duoss, J. D. Kuntz,
Chem. Eng. J. 2019, 375, 121959. C. M. Spadaccini, M. A. Worsley, Y. Li, Nano Lett. 2016, 16, 3448.
[87] Y. Li, H. Xie, J. Li, Y. Bando, Y. Yamauchi, J. Henzie, Carbon 2019, [122] C. Y. Foo, H. N. Lim, M. A. Mahdi, M. H. Wahid, N. M. Huang, Sci.
152, 688. Rep. 2018, 8, 7399.
[88] R. Jia, G. Shen, F. Qu, D. Chen, Energy Storage Mater. 2020, 27, 169. [123] A. Azhari, E. Marzbanrad, D. Yilman, E. Toyserkani, M. A. Pope,
[89] R. Jia, G. Shen, F. Qu, D. Chen, Energy Storage Mater. 2020, 27, 169. Carbon 2017, 119, 257.
[90] Y. Lu, Z. Lou, K. Jiang, D. Chen, G. Shen, Mater. Today Nano 2019, 8, [124] W. Li, Y. Li, M. Su, B. An, J. Liu, D. Su, L. Li, F. Li, Y. Song, J. Mater.
100050. Chem. A 2017, 5, 16281.
[91] P. Zhang, F. Wang, S. Yang, G. Wang, M. Yu, X. Feng, Energy Storage [125] Y. Chyan, R. Ye, Y. Li, S. P. Singh, C. J. Arnusch, J. M. Tour, ACS Nano
Mater. 2020, 28, 160. 2018, 12, 2176.
[92] P. Zhang, F. Zhu, F. Wang, J. Wang, R. Dong, X. Zhuang, [126] W. Gao, N. Singh, L. Song, Z. Liu, A. L. M. Reddy, L. Ci, R. Vajtai,
O. G. Schmidt, X. Feng, Adv. Mater. 2017, 29, 1604491. Q. Zhang, B. Wei, P. M. Ajayan, Nat. Nanotechnol. 2011, 6, 496.
[93] Z. Hao, L. Xu, Q. Liu, W. Yang, X. Liao, J. Meng, X. Hong, L. He, [127] M. F. El-Kady, R. B. Kaner, Nat. Commun. 2013, 4, 1475.
L. Mai, Adv. Funct. Mater. 2019, 29, 1808470. [128] V. Strong, S. Dubin, M. F. El-kady, A. Lech, Y. Wang, B. H. Weiller,
[94] D. Zhao, W. Chang, C. Lu, C. Yang, K. Jiang, X. Chang, H. Lin, R. B. Kaner, ACS Nano 2012, 6, 1395.
F. Zhang, S. Han, Z. Hou, X. Zhuang, Small 2019, 15, 1901494. [129] J. Lin, Z. Peng, Y. Liu, F. Ruiz-Zepeda, R. Ye, E. L. G. Samuel,
[95] H. J. In, S. Kumar, Y. Shao-Horn, G. Barbastathis, Appl. Phys. Lett. M. J. Yacaman, B. I. Yakobson, J. M. Tour, Nat. Commun. 2015,
2006, 88, 83104. 5, 1.
[96] J. H. Sung, S. J. Kim, S. H. Jeong, E. H. Kim, K. H. Lee, J. Power [130] B. Zheng, T. Huang, L. Kou, X. Zhao, K. Gopalsamy, C. Gao, J. Mater.
Sources 2006, 162, 1467. Chem. A 2014, 2, 9736.
[97] Z. Zhu, R. Kan, S. Hu, L. He, X. Hong, H. Tang, W. Luo, Small 2020, [131] W. Cai, T. Lai, J. Ye, J. Mater. Chem. A 2015, 3, 5060.
16, 2003251. [132] W. Liu, Y. Feng, X. Yan, J. Chen, Q. Xue, Adv. Funct. Mater. 2013, 23,
[98] J. Chen, C. Li, G. Shi, J. Phys. Chem. Lett. 2013, 4, 1244. 4111.
[99] R. Raccichini, A. Varzi, S. Passerini, B. Scrosati, Nat. Mater. 2015, 14, [133] W. Liu, X. Yan, J. Chen, Y. Feng, Q. Xue, Nanoscale 2013, 5, 6053.
271. [134] X. Wang, F. Wan, L. Zhang, Z. Zhao, Z. Niu, J. Chen, Adv. Funct.
[100] A. L. Ivanovskii, Russ. Chem. Rev. 2012, 81, 571. Mater. 2018, 28, 1707247.
[101] M. F. El-Kady, V. Strong, S. Dubin, R. B. Kaner, Science 2012, 335, [135] J. Yun, D. Kim, G. Lee, J. S. Ha, Carbon 2014, 79, 156.
1326. [136] Z. S. Wu, K. Parvez, X. Feng, K. Müllen, J. Mater. Chem. A 2014, 2,
[102] S. Arunachalam, B. Kirubasankar, D. Pan, H. Liu, C. Yan, Z. Guo, 8288.
S. Angaiah, Green Energy Environ. 2020, 5, 259. [137] D. Qi, Z. Liu, Y. Liu, W. R. Leow, B. Zhu, H. Yang, J. Yu, W. Wang,
[103] B. Kirubasankar, M. Narayanasamy, J. Yang, M. Han, W. Zhu, Y. Su, H. Wang, S. Yin, X. Chen, Adv. Mater. 2015, 27, 5559.
S. Angaiah, C. Yan, Appl. Surf. Sci. 2020, 534, 147644. [138] J. J. Yoo, K. Balakrishnan, J. Huang, V. Meunier, B. G. Sumpter,
[104] H. Pan, D. Wang, Q. Peng, J. Ma, X. Meng, Y. Zhang, Y. Ma, S. Zhu, A. Srivastava, M. Conway, A. L. Mohana Reddy, J. Yu, R. Vajtai,
D. Zhang, ACS Appl. Mater. Interfaces 2018, 10, 10157. P. M. Ajayan, Nano Lett. 2011, 11, 1423.
[105] C. Gao, K. Chen, Y. Wang, Y. Zhao, L. Qu, ChemSusChem 2020, 13, [139] G. Xiong, C. Meng, R. G. Reifenberger, P. P. Irazoqui, T. S. Fisher,
1255. Energy Technol. 2014, 2, 897.
[106] W. J. Hyun, E. B. Secor, C. H. Kim, M. C. Hersam, L. F. Francis, [140] Z. Niu, L. Zhang, L. Liu, B. Zhu, H. Dong, X. Chen, Adv. Mater. 2013,
C. D. Frisbie, Adv. Energy Mater. 2017, 7, 1700285. 25, 4035.
[107] S. Wang, N. Liu, J. Tao, C. Yang, W. Liu, Y. Shi, Y. Wang, J. Su, L. Li, [141] T. Purkait, G. Singh, D. Kumar, M. Singh, R. S. Dey, Sci. Rep. 2018, 8,
Y. Gao, J. Mater. Chem. A 2015, 3, 2407. 640.
[108] Y. Xu, I. Hennig, D. Freyberg, A. James Strudwick, M. Georg Schwab, [142] C. Liu, H. Liang, D. Wu, X. Lu, Q. Wang, Adv. Electron. Mater. 2018,
T. Weitz, K. Chih-Pei Cha, J. Power Sources 2014, 248, 483. 4, 1800092.
[109] C. Zhao, C. Wang, R. Gorkin, S. Beirne, K. Shu, G. G. Wallace, [143] D. Shen, G. Zou, L. Liu, W. Zhao, A. Wu, W. W. Duley, Y. N. Zhou,
Electrochem. commun. 2014, 41, 20. ACS Appl. Mater. Interfaces 2018, 10, 5404.
[110] T. S. Tran, N. K. Dutta, N. R. Choudhury, Adv. Colloid Interface Sci. [144] J. M. Munuera, J. I. Paredes, M. Enterría, S. Villar-Rodil, A. G. Kelly,
2018, 261, 41. Y. Nalawade, J. N. Coleman, T. Rojo, N. Ortiz-Vitoriano, A. Martínez-
[111] H. Li, J. Liang, Adv. Mater. 2020, 32, 1805864. Alonso, J. M. D. Tascón, ACS Appl. Mater. Interfaces 2020, 12, 494.
[112] J. Wang, F. Li, F. Zhu, O. G. Schmidt, Small Methods 2018, 3, [145] S. Sollami Delekta, K. H. Adolfsson, N. Benyahia Erdal,
1800367. M. Hakkarainen, M. Östling, J. Li, Nanoscale 2019, 11, 10172.
[113] Y. Xu, M. G. Schwab, A. J. Strudwick, I. Hennig, X. Feng, Z. Wu, [146] P. Yadav, A. Basu, A. Suryawanshi, O. Game, S. Ogale, Adv. Mater.
K. Müllen, Adv. Energy Mater. 2013, 3, 1035. Interfaces 2016, 3, 1.
[147] Z. Peng, R. Ye, J. A. Mann, D. Zakhidov, Y. Li, P. R. Smalley, J. Lin, [173] Q. Yin, D. Li, J. Zhang, Y. Zhao, C. Wang, J. Han, Appl. Surf. Sci.
J. M. Tour, ACS Nano 2015, 9, 5868. 2019, 487, 1.
[148] Z. S. Wu, Y. Z. Tan, S. Zheng, S. Wang, K. Parvez, J. Qin, X. Shi, [174] G. Qu, J. Cheng, X. Li, D. Yuan, P. Chen, X. Chen, B. Wang, H. Peng,
C. Sun, X. Bao, X. Feng, K. Müllen, J. Am. Chem. Soc. 2017, 139, 4506. Adv. Mater. 2016, 28, 3646.
[149] G. Wu, P. Tan, X. Wu, L. Peng, H. Cheng, C. F. Wang, W. Chen, [175] H. U. Lee, S. W. Kim, J. Mater. Chem. A 2017, 5, 13581.
Z. Yu, S. Chen, Adv. Funct. Mater. 2017, 27, 1. [176] Z. S. Wu, K. Parvez, S. Li, S. Yang, Z. Liu, S. Liu, X. Feng, K. Müllen,
[150] A.-K. Lu, H.-Y. Li, Y. Yu, J. Mater. Chem. A 2019, 7, 7852. Adv. Mater. 2015, 27, 4054.
[151] A. H. Siddique, S. W. Bokhari, R. Butt, S. Jiang, W. Chen, X. Zhou, [177] X. Tian, B. Xiao, X. Xu, L. Xu, Z. Liu, Z. Wang, M. Yan, Q. Wei, L. Mai,
Z. Liu, J. Mater. Sci. 2020, 55, 309. Nano Res. 2016, 9, 1012.
[152] J. Lin, C. Zhang, Z. Yan, Y. Zhu, Z. Peng, R. H. Hauge, D. Natelson, [178] Z. Liu, S. Liu, R. Dong, S. Yang, H. Lu, A. Narita, X. Feng, K. Müllen,
J. M. Tour, Nano Lett. 2013, 13, 72. Small 2017, 13, 1.
[153] X. Mao, J. Xu, X. He, W. Yang, Y. Yang, L. Xu, Y. Zhao, Y. Zhou, Appl. [179] K. Gholami Laelabadi, R. Moradian, I. Manouchehri, ACS Appl.
Surf. Sci. 2018, 435, 1228. Energy Mater. 2020.
[154] E. A. M. Smith, Y. Liu, C. Stirling, D. J. Watson, R. C. T. Slade, [180] Z. Wang, Q. Zhang, S. Long, Y. Luo, P. Yu, Z. Tan, J. Bai, B. Qu,
J. Chen, C. Crean, Electrochim. Acta 2019, 317, 348. Y. Yang, J. Shi, H. Zhou, Z. Y. Xiao, W. Hong, H. Bai, ACS Appl.
[155] M. P. Browne, E. Redondo, M. Pumera, Chem. Rev. 2020, 120, 2783. Mater. Interfaces 2018, 10, 10437.
[156] X. Tang, H. Zhou, Z. Cai, D. Cheng, P. He, P. Xie, D. Zhang, T. Fan, [181] X. Shi, L. Tian, S. Wang, P. Wen, M. Su, H. Xiao, P. Das, F. Zhou,
ACS Nano 2018, 12, 3502. J. Energy Chem. 2021, 52, 284.
[157] W. Zhang, Y. Lei, F. Ming, Q. Jiang, P. M. F. J. Costa, H. N. Alshareef, [182] C. Yang, K. S. Schellhammer, F. Ortmann, S. Sun, R. Dong,
Adv. Energy Mater. 2018, 8, 1801840. M. Karakus, Z. Mics, M. Löffler, F. Zhang, X. Zhuang,
[158] Y. Wang, Y. Zhang, J. Liu, G. Wang, F. Pu, A. Ganesh, C. Tang, X. Shi, E. Cánovas, G. Cuniberti, M. Bonn, X. Feng, Angew. Chem., Int.
Y. Qiao, Y. Chen, H. Liu, C. Kong, L. Li, Energy Storage Mater. 2020, Ed. 2017, 56, 3920.
30, 412. [183] K. Jiang, I. A. Baburin, P. Han, C. Yang, X. Fu, Y. Yao, J. Li,
[159] Y. Q. Li, X. M. Shi, X. Y. Lang, Z. Wen, J. C. Li, Q. Jiang, Adv. Funct. E. Cánovas, G. Seifert, J. Chen, M. Bonn, X. Feng, X. Zhuang,
Mater. 2016, 26, 1830. Adv. Funct. Mater. 2020, 30, 1908243.
[160] J. Zhang, X. Yang, Y. He, Y. Bai, L. Kang, H. Xu, F. Shi, Z. Lei, [184] W. Yan, J. Li, G. Zhang, L. Wang, D. Ho, J. Mater. Chem. A 2020, 8,
Z. H. Liu, J. Mater. Chem. A 2016, 4, 9088. 554.
[161] S. Gu, Z. Lou, L. Li, Z. Chen, X. Ma, G. Shen, Nano Res. 2016, 9, 424. [185] K. Vijaya Sankar, R. Kalai Selvan, Electrochim. Acta 2016,
[162] B. Shen, J. Lang, R. Guo, X. Zhang, X. Yan, ACS Appl. Mater. 213, 469.
Interfaces 2015, 7, 25378. [186] J. Qin, F. Zhou, H. Xiao, R. Ren, Z. S. Wu, Sci. China Mater. 2018, 61,
[163] A. Morag, J. Y. Becker, R. Jelinek, ChemSusChem 2017, 10, 2736. 233.
[164] W. Liu, C. Lu, X. Wang, R. Y. Tay, B. K. Tay, ACS Nano 2015, 9, 1528. [187] K. S. Kumar, N. Choudhary, Y. Jung, J. Thomas, ACS Energy Lett.
[165] H. U. Lee, C. Park, J.-H. Jin, S. W. Kim, J. Power Sources 2020, 453, 2018, 3, 482.
227898. [188] G. Sun, X. Zhang, R. Lin, J. Yang, H. Zhang, P. Chen, Angew. Chem.,
[166] B. D. Boruah, A. Maji, A. Misra, ACS Appl. Mater. Interfaces 2018, 10, Int. Ed. 2015, 54, 4651.
15864. [189] S. E. Moosavifard, J. Shamsi, M. K. Altafi, Z. S. Moosavifard, Chem.
[167] W. Wang, L. Lu, Y. Xie, W. Yuan, Z. Wan, Y. Tang, K. S. Teh, Adv. Commun. 2016, 52, 13140.
Mater. Technol. 2020, 5, 1. [190] M. Wei, X. Wu, Y. Yao, S. Yu, R. Sun, C. Wong, ACS Sustainable
[168] L. Zhang, Z. Chen, S. Zheng, S. Qin, J. Wang, C. Chen, D. Liu, Chem. Eng. 2019, 7, 19779.
L. Wang, G. Yang, Y. Su, Z.-S. Wu, X. Bao, J. Razal, W. Lei, [191] Q. Jiang, Y. Lei, H. Liang, K. Xi, C. Xia, H. N. Alshareef, Energy
J. Mater. Chem. A 2019, 7, 14328. Storage Mater. 2020, 27, 78.
[169] N. Kurra, Q. Jiang, H. N. Alshareef, Nano Energy 2015, 16, 1. [192] Y. Yue, N. Liu, Y. Ma, S. Wang, W. Liu, C. Luo, H. Zhang, F. Cheng,
[170] L. Li, J. Zhang, Z. Peng, Y. Li, C. Gao, Y. Ji, R. Ye, N. D. Kim, J. Rao, X. Hu, J. Su, Y. Gao, ACS Nano 2018, 12, 4224.
Q. Zhong, Y. Yang, H. Fei, G. Ruan, J. M. Tour, Adv. Mater. [193] C. Couly, M. Alhabeb, K. L. Van Aken, N. Kurra, L. Gomes,
2016, 28, 838. A. M. Navarro-Suárez, B. Anasori, H. N. Alshareef, Y. Gogotsi,
[171] G. W. Huang, N. Li, Y. Du, Q. P. Feng, H. M. Xiao, X. H. Wu, S. Y. Fu, Adv. Electron. Mater. 2018, 4, 1700339.
ACS Appl. Mater. Interfaces 2018, 10, 723. [194] S. Zheng, C. (John) Zhang, F. Zhou, Y. Dong, X. Shi,
[172] S. Shahrokhian, L. Naderi, R. Mohammadi, ACS Sustainable Chem. V. Nicolosi, Z.-S. Wu, X. Bao, J. Mater. Chem. A 2019, 7,
Eng. 2018, 6, 14574. 9478.
Balakrishnan Kriubasankar obtained his Ph.D. (2019) and M.Tech. (2013) in Nanoscience and
Technology at Pondicherry University. He obtained his B.Tech. (2011) in Chemical Engineering at
Pondicherry Engineering College. His research interests mainly focus on the synthesis of MXene,
transition metal chalcogenides, graphene and its inorganic analogues for the development of asymmetric,
and flexible microsupercapacitors.
Balakrishnan Balan is pursuing his Ph.D in Nanoscience and Technology under the supervision Professor
A. Subramania at Pondicherry University, India. He received his M.Tech. (2018) in Nanoscience and
Technology and B.Tech. (2015) in Electronics and Communication at Pondicherry University. His
research is mainly focused on the development of 2D materials (MXene, graphene, TMD) for printable
microsupercapacitors.
Chao Yan obtained his Ph.D. degree from the Institute of Chemistry, Chinese Academy of Science (CAS)
in 2007. He joined Jiangsu University of Science and Technology (JUST) in 2013. He is now a Professor
at the School of Materials Science and Engineering in JUST. His research interests include functional
nanocomposites and carbon materials for energy conversion and storage devices such as supercapacitor
and multivalent metal-ion batteries.
Subramania Angaiah is currently working as a professor at the Centre for Nanoscience and Technology,
Pondicherry University, India. He obtained his Ph.D. degree from Alagappa University & CSIR-CECRI
(2001) and his postdoctoral training from the Korean Institute of Science and Technology (KIST), Seoul,
South Korea. His current research interests include the development of nanostructured materials for
metal-ion batteries, supercapacitors, quantum dot sensitized solar cells, dye-sensitized solar cells and
perovskite solar cells.

2021ReviewG-MSCsente 202000844

Uploaded by

Copyright:

Available Formats

2021ReviewG-MSCsente 202000844

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2021ReviewG-MSCsente 202000844

Uploaded by

Copyright:

Available Formats

REVIEW

Recent Progress in Graphene-Based Microsupercapacitors

pseudocapacitors.[13–17] The electrode

Energy Technol. 2021, 2000844 2000844 (1 of 24) © 2021 Wiley-VCH GmbH

Energy Technol. 2021, 2000844 2000844 (2 of 24) © 2021 Wiley-VCH GmbH

Z t2 which seems to be a vertical sandwich-type structure as shown

Energy Technol. 2021, 2000844 2000844 (3 of 24) © 2021 Wiley-VCH GmbH

Table 1. Overview of various processing techniques of graphene MSCs.

Technique Advantage Disadvantage Dimension Industrialization Trend Precision Cost

Printing Simple Ink processing 2D/3D Large Yes Medium Low

Energy Technol. 2021, 2000844 2000844 (4 of 24) © 2021 Wiley-VCH GmbH

Energy Technol. 2021, 2000844 2000844 (5 of 24) © 2021 Wiley-VCH GmbH

Energy Technol. 2021, 2000844 2000844 (6 of 24) © 2021 Wiley-VCH GmbH

Energy Technol. 2021, 2000844 2000844 (7 of 24) © 2021 Wiley-VCH GmbH

4.4. Electrodeposition Technique 4.5. Photolithography Technique

Energy Technol. 2021, 2000844 2000844 (8 of 24) © 2021 Wiley-VCH GmbH

Energy Technol. 2021, 2000844 2000844 (9 of 24) © 2021 Wiley-VCH GmbH

To improve the electrochemical properties of graphene nano- 5.1.3. 3D Printed Graphene

(1-ethyl-3-methylimidazolium bis(triﬂuoromethylsulfonyl)imide modiﬁcation of composite electrode. MSC shows an areal spe-

(Figure 15). This MSC system manifests an areal capacitance

CP is a pseudocapacitive material combined with graphene to

6. Conclusion and Outlooks Acknowledgements

You might also like