Review

Cite This: ACS Energy Lett. 2018, 3, 482−495

Recent Advances in Two-Dimensional

Nanomaterials for Supercapacitor Electrode
Applications
Kowsik Sambath Kumar,†,‡ Nitin Choudhary,† Yeonwoong Jung,†,‡,§ and Jayan Thomas*,†,‡,⊥
†
NanoScience Technology Center, University of Central Florida, Orlando, Florida 32816, United States
‡
Department of Materials Science and Engineering, University of Central Florida, Orlando, Florida 32816, United States
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§
Department of Electrical and Computer Engineering, University of Central Florida, Orlando, Florida 32816, United States
⊥
CREOL, College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States

ABSTRACT: Supercapacitors represent a major technology to store

energy for many applications including electronics, automobiles,
military, and space. Despite their high power density, the energy
density in supercapacitors is presently inferior to that of the state-of-
the-art Li-ion batteries owing to the limited electrochemical perform-
ance exhibited by the conventional electrode materials. The advent of
two-dimensional (2D) nanomaterials has spurred enormous research
interest as supercapacitor electrode materials due to their fascinating
electrochemical and mechanical properties. This Review discusses
cutting-edge research on some of the key 2D supercapacitor electrode
materials including transition metal dichalcogenides, transition metal
oxides and hydroxides, MXenes, and phosphorene. Various synthetic
approaches, novel electrode designs, and microstructure tuning of
these 2D materials for achieving high energy and power densities are discussed.

high surface area and specific pore sizes.9,10 Another group of

T he world’s appetite for energy generation/storage from

renewable sources like solar, wind, and hydro is directly
driven by an exhaustive use of depleting fossil fuels.
Unfortunately, the intermittent nature of these renewable energy
sources makes them incompetent for the ever-increasing demand
for energy.1,3 The development of sustainable energy gen-
eration/storage systems and technologies is critical to reliably
cater the commercial/residential energy requirements and to
reduce the severe economic impacts of intermittent energy
sources.2 Rechargeable lithium-ion batteries (LIBs) have already
cemented their position as dominant energy sources powering
almost all forms of consumer electronics and electric vehicles
(EVs).4,5 Albeit the advantage of being a high energy density
provider, LIBs have the limitations of poor cycle life, low power
performance, and fire hazards.6 Supercapacitors, also known as
ultracapacitors, are currently being considered as an alternative
technology to LIBs because they are safer, pack ∼10 times more
power density, and last for several tens of thousands to millions of
charge/discharge cycles.7,8 Supercapacitor technology has been
improving at a fast pace, and they are highly reliable, as evidenced
by their use in the emergency exits of Airbus 380 aircrafts.3 One
of the major drawbacks of supercapacitors is their intrinsically
low energy density. The limitation is mainly attributed to the
purely electrostatic storage of charges in electrodes driven by
electrical double layer (EDL) formation, which strictly requires
electrochemical capacitors (ECs), broadly known as pseudoca-
pacitors, utilize fast and reversible faradaic reactions on the
electrode surface (or near-surface) for charge storage. Super-
capacitors with pseudocapacitive materials can achieve signifi-
cantly higher energy density compared to EDL capacitors as they
have a variety of oxidation states for redox charge transfer
reactions. However, relatively low electrical conductivity and
poor cycle stability due to slow ion transfer rates are limitations,
hampering their widespread commercial realization.11,12
The aforementioned limitations of the traditional ECs drive
significant research interests for the development of novel
electrode materials exhibiting excellent electrochemical perform-
ances to achieve high energy density. In recent years, two-
dimensional (2D) materials have drawn considerable attention as
supercapacitor electrode materials. 2D materials are ultrathin
layered crystals that show unusual physiochemical properties at
single- or few-atom thickness. 2D materials offer several key
advantages for next-generation electrochemical devices: (i)
atomically thin 2D nanosheets (NSs) provide a larger surface
area due to complete exposure of the surface atoms, (ii) the edge
Received: November 23, 2017
Accepted: January 22, 2018
Published: January 22, 2018

© 2018 American Chemical Society 482 DOI: 10.1021/acsenergylett.7b01169

ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters
sites in 2D NSs are chemically more reactive than basal planes
and the open van der Waals gaps enable the intercalation of
electrolyte ions, and (iii) the high mechanical strength and
flexibility at atomic dimensions allow them to be used in next-
generation wearable electronics. For example, graphene, a 2D
sheet of carbon, has remained a major source of scientific
fascination for energy storage over the past decade.13 Beyond
graphene, a large family of 2D materials have been emerging as
viable electroactive components for next-generation energy
storage devices while taking over the functions initially assigned
to LIBs. 2D transition metal dichalcogenides (TMDs) are
considered as major postgraphene contenders, which display
unique properties of large surface area and variable oxidation
states (e.g., +2 to +6 in MoS2), making them viable for both EDL
and faradaic charge storage mechanisms.14,15 The most
interesting attribute of 2D TMDs is their different polytype
(1T and 2H phase) structures, which show extraordinary
electrochemical performance and high operational voltage
windows.16 Transition metal oxides and hydroxides (TMOs
and TMHs), pseudocapacitive materials commonly used in bulk
forms, have intrinsically low electronic conductivities, limiting
fast ion diffusions, which makes them incompetent for high rate
performances. However, developing TMOs and TMHs in the
form of 2D nanostructures as nanofilms, NSs, nanoflakes,
nanoplatelets, nanopetals, nanobelts, etc. significantly alter their
inherent properties compared to their bulk counterparts. These
nanostructures often provide high conductivity, easy ion
diffusion, and improved mechanical integrity.17−20 It should be
noted that 2D TMOs and TMHs are not layered materials like
graphene and 2D TMDs, but a similar “2D” terminology is used
because of their ultrasmall (a few atom) thickness, exhibiting
extraordinary properties different from their bulk counterparts.
2D carbides and nitrides of transition metals, i.e., MXenes have
recently emerged as potential candidates for supercapacitor
electrodes due to their large surface-to-volume ratio, high
intrinsic conductivity, and abundant electrochemically active
sites, leading to significant intercalation or pseudocapacitance
through their transition metal chemistry.21 Phosphorene, an
analogue of graphene is emerging as a new 2D material,
possessing a puckered lamellae structure with weakly bonded
layers of phosphorus atoms.22 Despite its high electrical
conductivity, thermodynamic stability, and fast ion diffusivity,
phosphorene still remains largely unexplored as a supercapacitor
electrode material compared to other similar 2D materials.
Hence, an array of novel electrode materials exhibiting an EDLC
or pseudocapacitive charge storage mechanism are currently
being developed for high-performance supercapacitors. Beyond
materials development, synthesis of hybrid electrode materials
comprising of two or more electrochemically active 2D
nanomaterials (EDLC or pseudocapacitive) in the form of
composites, core/shell structures, and heterostructures have
been simultaneously pursued.23−25 These hybrid designs
introduce more electrochemical active sites, improved rate
capability, and enhanced cycle stability in the supercapacitors
owing to the synergistic effects enabled by high-quality
heterointerfaces, tunable electronic/chemical properties, and
high structural stabilities. Nevertheless, the construction of a
novel supercapacitor device configuration using these electrodes
is gaining significant attention as the energy density of the devices
relies not only on the capacitive performance of the electrode but
also on the higher operational voltage window (i.e., energy
density = (1/2)CV2, where C is the capacitance and V is the
operation voltage).8 For example, an asymmetric supercapacitor
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(ASC) device configuration utilizing two dissimilar electrodes
having dissimilar voltage windows has enabled a significant boost
in the energy density of supercapacitors in the past few years.26,27
2D TMOs and TMHs are not layered
materials like graphene and 2D TMDs,
but a similar “2D” terminology is used
because of their ultrasmall (a few atom)
thickness, exhibiting extraordinary
properties different from their bulk
counterparts.
This Review emphasizes the recent developments of novel 2D
electrode materials such as TMDs, TMOs and TMHs, MXenes,
and phosphorene and their electrochemical performances for
developing high energy density supercapacitor electrodes and
devices. The impact of crystal structures, crystalline phases, and
electrical/chemical properties inherent to these materials on the
supercapacitor electrode performances is discussed in detail. We
also deliberate how the characteristic properties of these
materials such as specific surface area, electrical conductivity,
and porosity can be tuned by engineering their nanostructures
into different form factors such as quantum dots, nanospheres,
nanowires, and nanorods. Design principles for rationally
integrating 2D materials with other electroactive materials to
achieve hybrid electrodes (composites, core/shell, and three-
dimensional (3D) nanostructures) are also highlighted.
(1) 2D Transition Metal Dichalcogenide (TMD) Electrodes. 2D
TMDs are layered materials in which a unit cell is composed of a
transition metal (M) layer sandwiched between two chalcogen
(X) layers in the form of MX2 (where M = Mo or W and X = S,
Se, or Te).28,29 The large surface area and variable oxidation
states in TMDs allow electrical double layer and fast/reversible
redox charge storage mechanisms. In addition, 2D TMDs exhibit
high electrochemical activity derived from their edge sites, which
offer large energy storage capability in supercapacitors.23,30−32
Despite a plethora of research conducted on monolithic 2D
TMDs based supercapacitor electrodes, their electrochemical
performance is often limited by poor cycle life, inherently low
electrical conductivity, large volume change during cycling, and
restacking.33,34 For example, sheet-like morphology of MoS2
proposed by Soon et al.32 provided a large surface area for double
layer storage; however, owing to its poor electrical conductivity,
it exhibited a low specific capacitance of ∼100 F g−1 at a scan rate
of 1 mV s−1. To circumvent these issues, 2D TMDs have been
mixed, wrapped, or deposited with highly conductive/electro-
active materials such as carbonaceous materials and conducting
polymers (CPs) using various top-down/bottom-up synthetic
techniques and their combinatorial approaches.35−42 Most
notably, the development of metallic TMD nanomaterials, as
discussed later in this section, are revolutionizing supercapacitor
research by offering exceptionally high electronic/ionic transport
and unprecedented charge storage ability.16,43,44
(1.1) TMDs/Carbonaceous Materials Hybrids. Typically,
carbonaceous materials like graphene, carbon nanotubes
(CNTs), carbon aerogel, etc. have high electrical conductivity
and surface area. Developing TMD hybrids or composite
materials with carbon-based materials provides a synergistic
effect of the two materials; carbon offers conductive channels and
enhancing interfacial contact, while TMDs contribute a short ion
diffusion path and successive short electron transport path, thus
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Figure 1. Different hybrid designs for high-performance TMDs supercapacitors. SEM images of (a) aligned MWCNT sheets, (b) MWCNT/MoS2
hybrids, and (c) tightly knotted MoS2/MWCNT and rGO/MWCNT fibers. (d) CV curves of rGO/MWCNT (cathode) and MoS2-rGO/
MWCNT (anode) in different voltage windows. (e) Cycle test of the fiber-based asymmetric device at a current density of 0.55 A cm−3. Adapted
with permission from ref 48, Copyright 2015 Wiley Online Library. (f) SEM and TEM images showing the formation of PANI nanoneedles on
MoS2 NSs. (g) Ragone plot showing the energy and power density at different voltage windows. (h) Schematic representation of facile H+ ion
intercalation into a MoS2/PANI composite. Adapted with permission from ref 24, Copyright 2011 Wiley Online Library.

enhancing overall electrochemical performance.45,46 A 3D
nanocomposite of MoS2/MWCNT (multiwall carbon nano-
tube) prepared by a facile one-pot L-cysteine-assisted hydro-
thermal process offered a large surface area and fast ionic
transport properties and delivered a high specific capacitance of
452.7 F g−1 with 95.8% retention after 1000 cycles.47 Almost
three times increase in capacitance (149.6 to 452.7 F g−1) was
observed in the composite compared to bare MoS2. Another
interesting electrode was designed by incorporating 2D MoS2
and reduced graphene oxide (rGO) NSs into aligned MWCNT
fibers.48 Figure 1a−c shows the scanning electron microscopy
(SEM) images of the aligned MWCNT fibers and their hybrids
with MoS2 and rGO. The solid-state supercapacitor fabricated
using a MoS2-rGO/MWCNT fiber electrode operates at a stable
potential window of 1.4 V, as shown by the CV curves in Figure
1d. Moreover, the device yields 100% Coulombic efficiency in
bending state even after 7000 cycles (Figure 1e). A high energy
density of 78.9 Wh kg−1 and an operational voltage window of 2.0
V have been reported in an ASC based on flower-like MoS2
grown on graphene NSs (GNSs) and MnO2/graphene hybrid
electrodes.49 This is an impressive achievement because the
energy density of the supercapacitor is approaching closer to thin
film LIBs (∼100 Wh kg−1).5
484
(1.2) TMDs/Conductive Polymers (CPs) Hybrids. CPs are
another promising additive that significantly enhances the
capacitive performance of 2D TMDs owing to their high
redox-active capacitance, moderately high electrical conductivity,
low cost, and high intrinsic flexibility.50,51 In situ polymerization
methods have been mainly employed to synthesize TMDs/CPs
hybrids as this method yields a better dispersion of TMD flakes in
CPs while inhibiting restacking of TMDs layers.52 Controlled
growth of polyaniline (PANI) nanowires on internal and external
faces of the 3D tubular MoS2 have been reported via oxidative
polymerization of aniline monomers. The hybrid electrode
exhibited a faradaic behavior with a high specific capacitance of
552 F g−1 at a current density of 0.5 A g−1. The improved
electrochemical performance was attributed to the unique 3D
tubular design that facilitates access of electrolyte ions to the
active sites of the electrode surface.53,54 Following a similar
approach, the morphological tuning of 2D MoS2 NSs was
achieved24 in which 1D PANI nanoneedle arrays vertically stand
on either side of the exfoliated 2D MoS2 NSs, as shown in SEM
and transmission electron microscopy (TEM) images in Figure
1f. This highly electrochemically active 2D MoS2@PANI
composite with large surface area and good electrical
conductivity yields a high specific capacitance of 853 F g−1 at a
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Figure 2. (a) SEM side view of the stacked 1T-MoS2 layers. (b) Volumetric capacitance of the 1T-MoS2 electrode at different scan rates and in
different electrolytes. (c) Cyclic stability test of 1T-MoS2 in different electrolytes. Adapted with permission from ref 16, Copyright 2015, Nature
Publishing Group. (d) SEM image of the VS2·3NH3 precursor with the inset showing a flake thickness of about 110 nm. (e) HR-TEM image of the
exfoliated VS2 NSs along (001) facets. (f) Specific capacitance and Coulombic efficiency of the metallic VS2 electrode. Adapted with permission
from ref 43, Copyright 2011, American Chemical Society.

Figure 3. (a) Specific capacitance vs scan rate of the 2D MnO2 nanosheets; the inset is the capacitance versus discharging current density.
Photographs of the (b) “panda” asymmetric MS/GA supercapacitor lighting up a red light-emitting diode. (c) Electrodes demonstrating
mechanical flexibility. Adapted with permission from ref 18, Copyright 2013 Springer Nature Publishing Group. (d) SEM image of Co3O4
nanoarrays. (e) Specific capacitance vs charge and discharge current density. Adapted with permission from ref 76, Copyright 2013 Springer
Nature Publishing Group.

(1.3) Metallic TMDs. Thus, far, supercapacitors based on

current density of 1 A g−1. A very impressive energy density of TMDs have mainly relied on the thermodynamically stable 2H
106 Wh kg−1 (Figure 1g,h) was also achieved. phase, which shows semiconducting yet poorly conducting
485 DOI: 10.1021/acsenergylett.7b01169
ACS Energy Lett. 2018, 3, 482−495
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Figure 4. (a) TEM image of single-layer β-Co(OH)2 and colloidal ethanol dispersion displaying the Tyndall effect. (b) Schematic illustration of
the hydrogen adsorption/desorption process in the single-layer β-Co(OH)2 electrode. Adapted with permission from ref 90, Copyright 2014
Wiley Online Library. (c) Schematic illustrating synthesis of α-Ni(OH)2 NSs. (d) FESEM image of α-Ni(OH)2 NSs. (e) Specific capacitance as a
function of current densities. Adapted with permission from ref 20, Copyright 2014 Nature Publishing Group.
characteristics. Recently, the introduction of a metallic 1T phase
in 2D TMDs is revolutionizing their potential for device
applications. The high electrical conductivity and excellent ion
intercalation capability in 1T-TMDs facilitate electron/ion
diffusion and dramatically enhance the specific capacitance.44
The Chhowalla research group16 demonstrated ∼107 times
higher electrical conductivity in 1T-MoS2 films as compared to
that of their semiconducting (2H-MoS2) counterparts. The
electrode assembled by stacking exfoliated 1T- 2D MoS2 NSs, as
shown in the SEM image of Figure 2a, yields a high capacitance in
the range of ∼400−700 Fcm−3 (Figure 2b) in various aqueous/
organic electrolytes. This electrode can operate at 3.5 V in
organic electrolytes and provides a Coulombic efficiency of
∼95% over 5000 charge/discharge cycles (Figure 2c). 2D
vanadium disulfide (VS2), an emerging metallic TMD, has been
reported to form in-plane supercapacitors.43 Figure 2d is an SEM
image of the ammonia-assisted VS2 flakes in bulk VS2 precursor,
where the thickness of an individual flake is ∼110 nm (inset of
Figure 2d). The 2D VS2 NSs extracted from these ammoniated
VS2 flakes were 4−5 atomic layers thick, as shown in Figure 2e.
Electrochemical characterizations revealed a specific capacitance
of 4760 μF cm−2 without any capacitance loss even after 1000
charge/discharge cycles (Figure 2f).
(2) 2D Transition Metal Oxides and Hydroxides Electrodes. 2D
oxides and hydroxides of transition metals are promising
supercapacitor electrode materials for their high chemical
stability/compatibility, high specific capacitance, and environ-
mental friendliness. In contrast to the bulk TMOs and TMHs,
which show poor rate performances due to intrinsically low
electronic conductivity impeding their fast ion diffusivity; their
2D counterparts provide an alternate route for compensating the
aforementioned shortcomings by offering short diffusion paths,
high electronic conductivity, and large surface areas. In the
following sections, we describe the development of 2D TMO-
and TMH-based supercapacitor electrode materials.
(2.1) 2D Transition Metal Oxides (TMOs). 2D TMOs (e.g.,
MnO2, Fe3O4, Co3O4, NiO, etc.) offer exciting properties as
promising supercapacitor electrode materials not only because of
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their intrinsically rich redox activity but also due to enlarged
surface areas endowing surface sites for EDL charge storage.55−62
Moreover, the thin/flexible TMO electrodes with high
mechanical and chemical stabilities provide the opportunity to
integrate them with next-generation flexible devices.63−66
Among various TMOs, manganese dioxide (MnO2) has been
extensively investigated owing to its low cost, nontoxicity, and
high theoretical capacitance (1370 F g−1).56,67,68 Ultrathin MnO2
NSs (MSs) (thickness ≈ 2 nm) synthesized using a soft template
method exhibited a specific capacitance of 774 F g−1 at a current
density of 0.1 A g−1 (Figure 3a).18 The ASCs fabricated using
MSs and graphene electrodes (GAs) exhibited a very high energy
density of 97.2 Wh kg−1 with 97% capacitance retention after
10000 cycles. These electrodes could be designed into various
pictures and patterns via screen printing (e.g., a panda design in
Figure 3b) and were made flexible (Figure 3c). In a recent
attempt,69 defects/vacancies were created in birnessite MnO2
(i.e., δ-MnO2, a 2D MnO2 allotrope with excellent capacitive
properties) in a controlled manner to achieve additional cation
intercalation sites. The exfoliated and reassembled δ-MSs form
3D macroporous electrodes, which provided a pseudocapaci-
tance of ≥300 F g−1 attributed to the synergistic effects between
the defect content and Mn redox, which worked together to
lower the charge transfer resistance and promote the ion
intercalation.
Despite some successful demonstrations, 2D MnO2-only
electrodes suffer from intrinsically poor electronic conductivities,
resulting in low power density and rate performance. Thereby,
MnO2 hybrids with conductive yet capacitive materials such as
graphene and CNTs have been proposed.70−73 For example, a
planar supercapacitor developed by using a 2D δ-MnO2/
graphene hybrid exhibits a high rate capability of ∼208 F g−1 at
10 A g−1 and capacitance retention of about 92% after 7000
charge/discharge cycles.63 Iron oxide (Fe3O4) has also been used
as an active 2D TMO component with carbon NSs and GNSs to
form hybrid composites.74,75 A 2D sandwich-like graphene-
supported Fe3O4 electrode formed by electrochemical method
exhibited a capacitance of 329 F g−1 at 0.5 A g−1 and an excellent
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ACS Energy Letters
energy density of 85 Whkg−1 at a power density of 2.4 kWKg−1.75
Uniformly distributed Fe3O4 on graphene sheets prevents
aggregation of Fe3O4 nanoparticles, offering a cycle life of 1000
cycles with 95% capacitance retention. Ultrathin cobalt oxide
(Co3O4) is another potential pseudocapacitive electrode material
offering low environmental impact, low cost, and great redox
activity. A uniform NS array composed of ∼5 μm long, ∼10 nm
thick Co3O4 NSs (Figure 3d) developed by a two-step
hydrothermal reaction exhibited a specific capacitance of 1782
F g−1 at a current density of 1.8 A g−1 (Figure 3e) and retained
>90% of initial capacitance after 2000 cycles.76 Porous 2D TMO-
based nanostructures play a critical role in boosting its surface
area, offering short pathways for charge transport and better
contact with electrolyte and accommodating substantial volume
expansion during cycling processes.77 Novel 3D porous Co3O4
NS structure exhibited a remarkable specific capacitance of 1500
F g−1 at 1 A g−1 and provided a high energy density of 15.4
Whkg−1 in ASC device configuration.78 In another report,
binder-free synthesis of mesoporous Co3O4 NS arrays on the Ni
foam using a two-step strategy of cobalt hydroxide (Co(OH)2)
electrodeposition followed by calcination witnessed a high
specific capacitance of 2735 F g−1 at a current density of 2 A g−1
in 2 M potassium hydroxide (KOH).79 Besides Co3O4, porous
hollow spheres enabled by randomly oriented 2D nickel oxide
(NiO) NS electrodes achieved a high specific capacitance of 600
F g−1 at 10 A g−1 and an excellent energy density of 19.44 Wh
kg−1.80 The good electrochemical performance in these electro-
des is attributed to the enhanced ionic transport of electrolyte
ions in the porous NiO NS network.
(2.2) 2D Transition Metal Hydroxides (TMHs). Similar to
TMOs, TMHs have been widely employed as high-performance
pseudocapacitive electrode materials in supercapacitors.81−85
However, their electrochemical performance is mainly dictated
by their morphology, and in bulk electrode structures, the
shortcoming was found to be due to the inefficient utilization of
active materials.27,86,87 Specifically, scaling of bulk TMHs to their
2D counterparts enables facile ion/electron transport, large
strain accommodation during cycling, and a reduced ion
diffusion barrier due to structural changes, which provides
excellent charge storage as well as high rate capability.20,88,89
TMHs of Co (i.e., Co(OH)2) and Ni (i.e., nickel hydroxide
(Ni(OH)2) have been mainly explored in their 2D nanostruc-
tures. For example, a solid-state ASC consisting of single layers of
β-Co(OH)2 (Figure 4a) as the cathode and N-doped graphene as
the anode delivered a high operation voltage of 1.8 V and an
exceptionally high energy/power density of 98.9 Wh kg−1/17981
W kg−1.90 Moreover, the device retained 93.2% capacitance after
10000 cycles. Performance akin to that of LIBs is attributed to the
100% exposure of surface hydrogen atoms by five-atom thick
Co(OH)2 single layers to serve as electroactive sites for
significant faradaic redox reactions, as demonstrated in the
schematic of Figure 4b. 2D Ni(OH)2 is another cost-effective
material that presents excellent electrochemical properties for
high energy density supercapacitors. Ultrathin, free-standing 2D
NSs (thickness < 2 nm) of α-Ni(OH)2 were prepared using a
microwave-assisted liquid-phase growth method.20 Figure 4c,d
shows the growth process and SEM image of the as-synthesized
α-Ni(OH)2 NSs. These ultrathin 2D nanostructures exposed the
majority of the atoms for surface-dependent electrochemical
reaction processes, exhibiting a maximum specific capacitance of
4172.5 F g−1 at a current density of 1 A g−1. Even at a higher rate
of 16 A g−1, the specific capacitance was maintained at 2680 F g−1
with 98.5% retention after 2000 cycles (Figure 4e).
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Despite remarkable capacitive performance exhibited by
single-component 2D TMHs like Co(OH)2 and Ni(OH)2,
these may suffer significant capacitance decay after prolonged
cycling at high current densities. To circumvent this issue,
hybrids of 2D TMHs are being developed by growing/mixing
them with highly conductive materials, metal oxides, or other 2D
TMHs. For instance, single-crystalline Ni(OH)2 nanoplates were
grown on 3D graphene sheet networks.91 The composite
delivered high specific and rate capacitances of ∼1335 F g−1 at
2.8 A g−1 and ∼953 F g−1 at 45.7 A g−1, respectively. The energy
density was estimated to be ∼37 Wh kg−1 at a power density of
∼10 kW kg−1. 2D TMH/TMH hybrid electrodes present
advanced supercapacitors due to their enhanced redox activity
bestowed by multiple redox reactions in each participating TMH.
2D porous Ni(OH)2-Co(OH)2 hybrids were facilely prepared in
ethylene glycol−water solution.92 These electrodes exhibit an
excellent specific capacitance of 1537 F g−1 at 0.5 A g−1 and
retained ∼1181 F g−1 even at a high current density of 10 A g−1.
The ASCs fabricated with carbonaceous electrodes achieved a
high energy density of 33.7 Wh kg−1 at a power density of 551 W
kg−1 and an operating voltage of 1.5 V. Moreover, an excellent
cycling stability with 109% capacitance retention after 10000
cycles was observed. A novel Ni(OH) 2 /Co(OH) 2 NS
architecture composed of electrodeposited Ni(OH)2 and
Co(OH)2 consecutive layers was recently developed.93 These
electrodes showed a specific capacitance of 1524 F g−1 at a
specific current of 1 A g−1. An ASC using Ni(OH)2/Co(OH)2 as
the positive electrode and carbon nanofoam paper as the negative
electrode yielded a specific energy density of 101.3 Wh g−1.
TMH−TMO hybrids have also been explored to achieve high
energy densities in supercapacitors. A hydrothermally grown
ultrathin Ni(OH)2−MnO2 hybrid NS array on 3D macroporous
nickel foam exhibits an ultrahigh specific capacitance of 2628 F
g−1.94 The highly hydrophilic and ultrathin nature of hybrid NSs
with high synergetic effects between Ni(OH)2 and MnO2 was
responsible for the outstanding electrochemical performance.
Nevertheless, the ASCs assembled using a Ni(OH)2−MnO2
cathode and rGO as the anode provided a very high energy
density of 186 Wh kg−1 and a power density of 778 W kg−1.
(3) MXene Electrodes. The major limitation of low electrical
conductivity in TMOs/TMHs needs modification of their
structural morphology or development of their composites
with highly conductive additives to effectively use them as
supercapacitor electrodes. However, a material with inherently
high electrical conductivity on its own holds great promise as an
excellent energy storage electrode. MXenes, an emerging class of
2D supercapacitor electrode material, possesses a high intrinsic
electronic conductivity, good hydrophilic nature, and excellent
mechanical stability.95,96 MXenes are few atoms thick transition
metal carbides, nitrides, or carbonitrides derived from the MAX
phase having a chemical composition of Mn+1AXn, where n = 1, 2,
or 3, M is an early transition metal, A is mostly group 13 and 14
elements of the periodic table, and X is C and/or N.97 MXenes,
developed by extracting A from the MAX phase, is denoted as
Mn+1XnTx, where T represents surface termination groups (−O,
−OH, and −F) left over from the etching process and x is the
number of terminating groups. Here, we describe several
significant developments in the MXene-based supercapacitors.
(3.1) Synthesis, Surface Modif ication, and Mass Loading.
Gogotsi’s group at Drexel University pioneered the development
of MXene-based supercapacitors.21,98 They exfoliated titanium
aluminum carbide (Ti3AlC2) in the presence of hydrofluoric acid
(HF) to produce 2D NSs of titanium carbide (Ti3C2) exhibiting
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graphene-like morphology with good chemical stability, electrical
conductivity, and high ductility. A free-standing conductive paper
made from these Ti3C2 MXene NSs exhibited a high volumetric
capacitance of 340 F cm−3 in KOH.98 Ghidiu et al. produced
freestanding Ti3C2 with intercalated water, adopting a much safer
route using a solution of lithium fluoride (LiF) and hydrochloric
acid (HCl) as an etchant.99 The MXene produced was a clay-like
paste that can be molded to yield various shapes with high
conductivity and can also be used as an ink to print MXene on
various substrates. Electrochemical performance of these Ti3C2
freestanding films in 1 M Na2SO4 exhibited a volumetric
capacitance of 900 F cm−3 at 20 mV s−1, a gravimetric capacitance
of 245 F g−1 at 2 mV s−1, and magnificent cycle stability (100%
capacitance retention after 10000 cycles). The outstanding
The outstanding performance of the LiF
+ HCl etched Ti3C2 compared to HF
etched Ti3C2 is attributed to preinter-
calated water and the smaller size of
the cation (H+) in the electrolyte.
performance of the LiF + HCl etched Ti3C2 compared to HF
etched Ti3C2 is attributed to preintercalated water and the
smaller size of the cation (H+) in the electrolyte. Another
approach to develop Ti3C2Tx films is a simple dropping-mild
baking method, which demonstrated high gravimetric capaci-
tances up to 499 F g−1 even with low mass loading.100
To study the effect of surface chemistry on capacitive
performance, Simon and co-workers101 modified Ti3C2Tx via
(i) delamination of Ti3C2Tx by intercalation of dimethyl
sulfoxide (d-Ti3C2) and (ii) chemical intercalation of K+ ion
using potassium hydroxide (KOH-Ti3C2) and potassium acetate
(KOAc-Ti3C2) (Figure 5a). Chemical intercalation of potassium
salts replaced terminal fluorine with oxygen-containing func-
tional groups, leading to a 4-fold increase in capacitance.
Delamination led to an increase in surface area, causing the d-
Ti3C2 to exhibit outstanding volumetric capacitance of 520 F
cm−3 and a gravimetric capacitance of 325 F g−1 at 2 mV s−1. This
work led to a new approach of modifying surface chemistry of
various MXenes to achieve better electrochemical performance.
Figure 5. (a) Schematic illustration of the modifications of Ti3C2Tx: delamination and intercalation of K+. Adapted with permission from ref 101,
Copyright 2014 Elsevier. (b) Cross-sectional SEM image of sandwich-like Ti3C2Tx/SWCNT. (c) Cycling stability of the sandwich-like Ti3C2Tx/
SWCNT electrode at 5 A g−1. (Inset) First three cycles of GCD. Adapted with permission from ref 114, Copyright 2014 Wiley Online Library.
488
Review
High mass loading of the active material is an important aspect
when it comes to practical application of supercapacitors. An
increase in material loading typically increases the resistance and
limits electrolyte accessibility, leading to poor capacitive
performance. Lin et al.102 discovered that Ti3C2 is exceptional
because its layered microstructure helps in the electrochemical
utilization of all of the Ti3C2 sheets and exhibits high electronic
conductivity. The electrode made from these NSs with a high
mass loading of 7.6 mg achieved an areal capacitance of 579 mF
cm−2 at 2 mV s−1 compared to 211 mF cm−2 with 1.8 mg of
material. Also, the good connectivity between Ti3C2 sheets
makes the equivalent series resistance (ESR) value of high mass
loading (0.90 Ω, 7.6 mg) Ti3C2 electrode material comparable to
that of the low mass loading (0.83 Ω, 1.8 mg) material. This mass
loading test opens up the significance of using 2D layered
nanomaterials for achieving high energy for practical applica-
tions.
(3.2) Flexible MXenes. Developing flexible energy storage
devices is highly necessary for designing next-generation smart
electronics and wearables.103−105 Peng et al.106 fabricated an all-
Ti3C2Tx solid-state interdigital microsupercapacitor (MSC) by
solution spray-coating of large size (3−6 mm laterally) HCl/LiF
etched Ti3C2Tx as the current collector, which was followed by
spray-coating of small size HCl/LiF etched Ti3C2Tx (∼1 mm)
with more defects and edges on top as the electroactive layer. The
device exhibited areal and volumetric capacitances of ∼27 mF
cm−2 and ∼357 F cm−3, respectively, at a scan rate of 20 mV s−1
with 100% capacitance retention after 10000 cycles at a scan rate
of 50 mV s−1. Recently, a symmetric solid-state flexible fiber-
based MXene supercapacitor107 was developed using Ti3C2Tx
flakes loaded on silver-plated nylon fibers as electrodes and a
polyvinyl alcohol (PVA)-H2SO4 hydrogel as the electrolyte. The
fabricated fiber device exhibited a high areal capacitance of 328
mF cm−2 with excellent cyclability, flexibility, knittability, and
cycle stability. The capacitance remained at least above 80%
under various deformation modes including bending, twisting,
and knotting. At a scan rate of 2 mV s−1, it showed an energy
density of 7.3 μWh cm−2 and a power density of 132 μW cm−2.
These results promise a plethora of opportunities for powering
wearable and flexible electronics applications employing MXenes
and their heterostructures.
(3.3) MXene-based Composites. Like other 2D materials,
restacking and irreversible aggregation of 2D NSs is a potential
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ACS Energy Letters
problem in MXene electrodes as well, which essentially diminish
the interlayer spacing and accessibility of ions for electrochemical
utilization. Interlayer spacing can be modulated by developing
MXene composites by incorporating species like polymers,108,109
carbon derivatives,110,111 and metal oxides108,112 into the layers.
These interlayer spacers prevent restacking of the MXene flakes
and thus increasing electrochemical utilization of the entire
surface of the material. A MAX phase−polymer composite was
first developed by Ling et al. using poly-
(diallyldimethylammonium chloride) (PDDA) and PVA.113
Ti3C2Tx films on their own possess excellent mechanical and
tensile strength (22 ± 2 MPa). Upon introducing PVA, the
Ti3C2Tx/PVA film exhibited a four times increase in tensile
strength. Introduction of PVA also prevented restacking and
increased interlayer spacing of Ti3C2Tx flakes, thus improving the
accessibility of ions to deep trap sites. The composite showed
maximum capacitance of 530 F cm−3 at 2 mV s−1. Zhao et al.114
prepared sandwich-like MXene/CNT composite electrodes by
alternate deposition of Ti3C2Tx flakes and CNT layers (Figure
5b). CNT provided faster diffusion paths and enlarged interlayer
spacing between the Ti3C2Tx flakes for cation intercalation. A
high volumetric capacitance of 350 F cm−3 at a 5 A g−1 current
density was achieved with no degradation even after 10000 cycles
for MXene/SWCNT papers (Figure 5c). Incorporation of rGO
into Ti3C2Tx flakes increased the interlayer spacing and exhibited
a volumetric capacitance of 435 F cm−3 at 2 mV s−1.
Despite the high areal and volumetric capacitance, MXenes
suffered from poor gravimetric capacitance because of their low
surface area (30 m2 g−1). Decorating MXenes with pseudoca-
pacitive materials improve the surface area considerably. The first
MnO2/MXene hybrids (MnO2/Ti3C2Tx) fabricated by direct
chemical synthesis evidence a large surface area of 183.8 m2 g−1
compared to pristine Ti3C2Tx (21.1 m2 g−1).115 Such an increase
in surface area enhances the effective contact of electrolyte and
active materials by trapping more electrolyte solution. This
provides superior pseudocapacitance and improves overall
cycling performance. Specific capacitance values of 77.5 and
210.9 F g−1 are obtained for symmetric supercapacitors of
Ti3C2Tx and MnO2/Ti3C2Tx samples, respectively, at a constant
scan rate of 10 mV s−1. At a constant power density of 20 kW
kg−1, the MnO2/Ti3C2Tx hybrid exhibited an energy density of
12.25 Wh kg−1 with good cyclic stability (88% capacitance
retention) after 10000 cycles. Hybrid electrodes of MXene with
titanium dioxide (TiO2) and MoO3 have also been devel-
oped.108,112 A hybrid of TiO2/Ti3C2Tx108 exhibited a gravimetric
capacitance of 143 F g−1, retaining ∼92% of its initial capacitance
after 6000 cycles. MoO3, being a highly electrochemically active
material, increases the specific surface area and active sites,
delivering a maximum capacitance of 151 F g−1 with 93.7%
capacitance retention after 8000 cycles of the charge−discharge
process.112
(4) Phosphorene Electrodes. Another recently emerging 2D
material for energy storage applications is phosphorene, a single
atomic layer of black phosphorus (BP) analogous to graphene.
Phosphorene, a puckered lamellae structure with weakly bonded
layers of phosphorus atoms via van der Waals interactions, shows
good electrical conductivity, thermodynamical stability, and fast
ion diffusivity. These properties make phosphorene an attractive
candidate for supercapacitor applications.22,116 Interestingly, a
flexible solid-state supercapacitor117 based on liquid phase
exfoliated phosphorene nanoflakes has been recently developed,
which exhibits an impressive volumetric capacitance of 17.78 F
cm−3 (59.3 F g−1) at 0.1 V s−1 and excellent rate capacitance while
489
Review
maintaining 1.43 F cm−3 (4.8 F g−1) of volumetric capacitance at
10 V s−1. Phosphorene electrode, even after prolonged (30000)
charge/discharge cycles, exhibits high mechanical stability,
maintaining its crystalline structure as investigated under TEM
with corresponding capacitance retention of 71.8%. Red
phosphorus (RP), one of the allotropes of phosphorus with
high theoretical specific capacitance (similar to BP)22 has been
used to make a hybrid electrode material composed of BP and
RP. A simple sonochemical process118 was followed to develop a
single elemental hybrid of BP and RP (BP/RP hybrid), and the
hybrid electrode was electrochemically tested in 0.1 M KOH
electrolyte. The BP/RP hybrid electrode demonstrated typical
EDLC behavior even at higher scan rates and yielded specific
capacitances of 60.1 and 41.6 F g−1 at 0.5 and 8 A g−1 current
densities, respectively. Hybridization of BP and RP facilitated fast
and short electronic/ionic transfer, leading to high reaction
kinetics with good cyclic stability. The hybrid cycled for 2000
cycles retained 83.3% of its initial capacitance, higher than that of
RP. Microsupercapacitors (MSCs) with a mask-assisted
interdigital electrode pattern have been fabricated using layer-
by-layer stacking of phosphorene NSs and electrochemically
exfoliated graphene (PG-MSCs) in ionic liquid electrolyte.119
The simplified mask-assisted development of PG-MSCs is
scalable for production of a serially interconnected MSC pack
and provides excellent flexibility, as shown in Figure 6a,b. MSCs
Figure 6. (a) Photograph of nine serially interconnected PG-MSCs.
(b) Flexibility and stability demonstration of PG interdigital
electrodes at a highly folded state with the inset showing electrodes
in the unfolding state. Reprinted with permission from ref 119,
Copyright 2017 American Chemical Society.
provided excellent electrochemical performance of 9.8 mF cm−2
and volumetric capacitance of 37.5 F cm−3 at 5 mV s−1 and
retained 94% of their initial capacitance under different bending
states. The excellent performance of PG-MSCs can be attributed
to the strong coupling of phosphorene and GNSs offering high
ionic accommodation and fast transport pathways and restricting
graphene restacking due to phosphorene. The graphene serves as
a mechanical skeleton, providing high-speed electron transfer
network. The remarkable electrochemical performance endowed
by a phosphorene-based supercapacitor is indicative of its
potential for widespread applications.
(5) Summary and Outlook. The post-graphene era witnesses
explosive development of a breadth of 2D inorganic nanoma-
terials for many current and future electronic/energy technol-
ogies. Electrochemical energy storage via supercapacitors is one
of the rapidly evolving thrust areas where these materials show
uncanny potential toward high energy density devices, replacing
traditional LIBs. In this Review, we summarize the major
advances of 2D inorganic materials such as TMDs, TMOs,
TMHs, MXenes, and phosphorene for energy storage in
supercapacitors. The use of 2D TMDs as supercapacitor
electrode materials is enabled by their large surface areas and
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ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters Review

Table 1. Various 2D Materials and Their Supercapacitor Performances

capacitance/scan rate or cycle test capacitance
2D family active material current density rate capability energy density retention (%)/cycles ref
TMDs MoS2 nanowall films 100 F g−1/1 mV s−1 32
TMDs/ MoS2/MWCNT nanocomposite 452 F g−1/1 A g−1 73.71% from 1 to 10 A g−1 95.8/1000 47
carbonaceous
hybrids
MoS2-rGO/MWCNT ∼6.2 F cm−3/0.07 A cm−3 61% from 0.07 to 3.3 A cm−3 ∼99/7000 48
flower-like MoS2/GNS 320 F g−1/2 A g−1; ASC: ∼50% from 2 to 20 A g−1 78.8 Wh kg−1 at 90/5000 49
142 F g−1/2 mV s−1 284.1 W kg−1
TMDs/CPs tubular MoS2/PANI nanowires 552 F g−1/0.5 A g−1 82% from 0.5 to 30 A g−1 79/6000 52
hybrids
MoS2 NSs @PANI nanoneedle arrays 853 F g−1/1 A g−1 106 Wh kg−1 at 83/4000 24
106 kW kg−1
metallic TMDs metallic 1T-WS2 nanoribbons 2813 μF cm−2/0.5 A m−2 ∼34/2000 44
metallic 1T-MoS2 NSs ∼400−700 F cm−3 0.016 Wh cm−3 at >93−97/5000 16
0.62 W cm−3
VS2 NSs 4760 μF cm−2 100/1000 43
(317 F cm−3)/0.1 A m−2
TMOs MSs 774 F g−1/0.1 A g−1; ASC: 76% from 2 to 50 mV s−1 97.2 Wh kg−1 >97/10000 18
175 F g−1 at 0.1 A g−1
δ-MSs ≥300 F g−1 69
δ-MnO2/graphene hybrid 267 F g−1/0.2 A g−1 77.9% from 0.2 to 10 A g−1 18.64 Wh kg−1 at 92/7000 63
12.6 kW kg−1
e-Fe3O4@rGO sheets 329 F g−1/0.5 A g−1 90% from 0.5 to 10 A g−1 85 Wh kg−1 at 95/1000 75
2.4 kW kg−1
ultrathin Co3O4 NSs 1782 F g−1/5 mA cm−2; ASC: 51% from 5 to 30 mA cm−2 134 Wh kg−1 at >90/2000 76
108 F g−1/5 mA cm−2 1111 W kg−1
2D Co3O4 by 3D interconnected 1500 F g−1/1 A g−1 55.2% from 1 to 10 A g−1 15.4 Wh kg−1 at 99.3/2000 78
nanoflakes 0.8 kW kg−1
Co3O4 NS arrays 2735 F g−1/2 A g−1 53.78% from 2 to 10 A g−1 99/3000 79
porous NiO hollow spheres 600 F g−1/10 A g−1 19.44 Wh kg−1 80
TMHs β-Co(OH)2 2028 F g−1/5 mV s−1 98.9 Wh kg−1 at 93.2/10000 90
17.981 kW kg−1
α-Ni(OH)2 NSs 4172 F g−1/1 A g−1 64.23% from 1 to 16 A g−1 98.5/2000 20
Ni(OH)2 nanoplates 1335 F g−1/2.8 A g−1 71.40% from 2.8 to 45.7 A g−1 37 Wh kg−1 at 100/2000 91
10 kW kg−1
Ni50Co50-LDH 1537 F g−1/0.5 A g−1; ASC−: 76.9% from 0.5 to 10 A g−1 33.7 Wh kg−1 at 80.3/1000 92
107.8 F g−1/1 mA cm−2 5.4 kW kg−1
Ni(OH)2/Co(OH)2 762 C g−1/1 A g−1 101.3 Wh g−1 93
ultrathin Ni(OH)2-MnO2 hybrid NS 2628 F g−1/3 A g−1; ASC: 5 50.53% from 3 to 20 A g−1 186 Wh kg−1 at ASC: 76/3000 94
arrays 38 F g−1/1.4 A g−1 778 W kg−1
MXene layered Ti3C2 340 F cm−3 100/10000 98
Ti3C2 clay 900 F cm−3/20 mV s−1; 100/10000 99
245 F g−1/2 mV s−1
Ti3C2 nanoflakes 499 F g−1/2 mV s−1 100/10000 100
d-Ti3C2 520 F cm−3 and 100/10000 101
325 F g−1/2 mV s−1
Ti3C2 579 mF cm−2/2 mV s−1 98/10000 102
flexible MXene Ti3C2Tx flakes ∼357 F cm−3/20 mV s−1 100/10000 106
Ti3C2Tx@ silver-plated nylon 328 mF cm−2/2 mV s−1 7.3 μWh cm−2 at ∼100/10000 107
132 μW cm−2
MXene Ti3C2Tx/PVA film 530 F cm−3/2 mV s−1 48.73% from 2 to 100 mV s−1 ∼85/10000 113
composites
1. Ti3C2Tx/SWCNT composite paper; 1. 345 F cm−3/5 A g−1; 1. ∼87% from 5 to 10 A g−1; 1. 100/10000; 114
2. Ti3C2Tx/rGO composite paper 2. 435 F cm−3/2 mV s−1 2. 74% from 2 to 200 mV s−1 2. 109/10000
MnO2/Ti3C2Tx hybrid 210.9 F g−1/10 mV s−1; 83% from 1 to 40 A g−1 12.25 Wh kg−1 at 88/10000 115
212.1 F g−1/1 A g−1 20 kW kg−1
TiO2/Ti3C2 nanocomposite 143 F g−1/5 mV s−1 82% from 5 to 200 mV s−1 92/6000 108
MoO3/Ti3C2Tx composite 151 F g−1/2 mV s−1 93.7/8000 112
phosphorene phosphorene nanoflakes 17.78 F cm−3 ∼9% from 0.1 to 10 V s−1 71.8/30000 117
(59.3 F g−1)/0.1 V s−1
BP/RP hybrid 60.1 F g−1/0.5 A g−1 69.2% from 0.5 to 8 A g−1 83.3/2000 118
phosphorene NSs 9.8 mF cm−2 or 11.6 mW cm−3 89.5/2000 119
37.5 F cm−3/5 mV s−1

variable oxidation states, which provide them the capability to
store charge via EDLs as well as by pseudocapacitance.
Moreover, the presence of active edge sites and weak van der
Waals gaps between the neighboring layers in 2D TMDs render
490
promising electrochemical performance. 2D nanostructures of
TMOs and TMHs not only provide large surface areas but a high
percentage of surface atoms enriched with redox activities are
exposed to electrolyte ions, leading to enhanced pseudocapaci-
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ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters
tive performance. Despite significant enhancement in the
performance of supercapacitors based on the 2D TMDs,
TMOs, and TMHs, the major intrinsic bottleneck that keeps
them from widespread practical applications is their low electrical
conductivity, which results in inferior pseudocapacitance. To
compensate the aforementioned demerits, these materials are
either incorporated into highly conductive/capacitive materials
like carbon materials and CPs or subjected to exotic nanoma-
terials engineering in various form factors such as porous
nanostructures, 1D/2D and 3D/2D morphologies, core/shell
designs, etc. For example, conducting graphene layers in these
hybrids act as fast electron transfer channels, preventing
restacking issues as well as showing high synergic effects with
pseudo-materials to exhibit high electrochemical performance.
Developing a porous electrode enhances the surface area and
interface contact between the electrode and electrolyte, which in
turn enhances the specific capacitance/energy density of
supercapacitors. In addition to the above approaches, hybrids
of 2D TMOs/TMHs, and 2D TMHs/TMHs have also been
developed to achieve advanced supercapacitor electrodes with
high redox activity and improved cycle life.
In recent years, supercapacitor research grew considerably due
to the emergence of the metallic phase in the existing 2D
materials or the advent of new metallic materials. For example,
2D TMDs in their metallic (1T) phase have shown exceptional
supercapacitor properties, which is benefited by the enhanced
conductivity of the network (i.e., 107 times greater than that of
the semiconducting 2H phase) and high hydrophilicity
enhancing its contact with aqueous electrolytes. 2D transition
metal carbides/nitrides (MXenes) are another emerging class of
novel pseudocapacitive electrode materials with extremely high
intrinsic electronic/ionic conductivity. The high surface
pseudocapacitive activity in MXenes demonstrates very high
intercalation capacitance (∼1000 F cm−3) in aqueous electro-
lytes. Moreover, MXene fillers are playing a key role in enhancing
the mechanical property and chemical stability of polymeric- and
metal oxide-based supercapacitor electrodes. Phosphorene, a 2D
allotrope of phosphorus, is showing great potential for high-
performance supercapacitors owing to its excellent electrical
conductivity (∼300 S m−1), large interlayer spacing (∼3.08 A),
high thermodynamic stability, and fast ion diffusivity. In addition,
the outstanding flexibility in phosphorene makes it viable for
flexible energy storage devices. A comparison of the electro-
chemical performance of all 2D materials discussed above is
presented in Table 1. Despite a plethora of research conducted in
the development of novel 2D nanomaterials discussed in this
Review, there are still many current and foreseen challenges as
well as future directions that might be considered to make these
materials viable for commercial energy storage technologies:
(5.1) Interface−Property and Performance Relationships in 2D
Hybrids. To leverage the optimum materials properties from the
constituent elements in 2D hybrids, it is imperative to
understand their interface relationships that govern the
physiochemical properties of the hybrids to exhibit enhanced
performances. Even though a large section of the scientific
community observes synergistic effects in terms of enhanced
electrochemical performances, the legitimate factors responsible
for the hybrids’ performance are still unknown. For example, how
do the interface atoms adjust their orientation, crystalline
structure, and layer number to exhibit high synergistic effects?
What are the fundamental atomistic parameters that define the
viability of distinct materials to construct highly compatible
hybrids and are these factors tunable/adjustable to leverage the
491
Review
best materials properties? What are the mechanical/chemical
binding principles of 2D materials with interacting materials and
how does the interface chemistry influence the overall electro-
chemical performance? Detailed/advanced studies using in situ
characterizations techniques are required to unveil the
fundamentals of hybrid interfaces.
(5.2) Metallic 2D Materials Need Further Development.
Although metallic 2D materials such as 1T-TMDs and MXenes
show enormous potential toward high energy density super-
capacitors owing to their intrinsically high electrical conductivity
as well as versatile transition metal chemistry to exhibit
pseudocapacitive charge storage, their research is still at the tip
of the iceberg. 1T-TMD fabrication is generally accompanied by
the formation of 2H counterparts, or an easy phase transition
occurs from the 1T to 2H phase in some cases. Therefore, proper
fabrication methods are required to achieve a stable/pure 1T
phase to access their real performance. MXene growth
techniques use toxic acids (e.g., HF), resulting in arbitrary
functionalization, which overshadows their real performance.
Hence, acid-free growth of MXenes and MXenes without surface
functionalization is required to leverage their intrinsic perform-
ance as electrode materials. Furthermore, the behavior of metallic
TMDs and MXenes with other capacitive materials such as CPs,
carbon materials, and TMOs/nitrides in the form of hybrids/
composites is less known. Such hybrids are expected to promote
the electron/ion conduction pathways by a manifold to achieve
high-performance supercapacitors.
(5.3) Need for Novel Electrolytes and Stability Issues. The limited
number of aqueous/nonaqueous electrolytes known to the
scientific community are becoming obsolete with the advent of
an array of novel 2D nanomaterials due to the novel
physiochemical properties of the surface atoms of newly
developed 2D electrode materials. For example, MXenes are
prone to easy oxidization in various aqueous electrolytes, which
results in an increase of resistance and capacitance decay during
cycling tests.98 Hence, there is a parallel need to develop
compatible electrolytes along with the development of novel 2D
electrode materials. On the other hand, novel electrodes like
phosphorene face stability issues under ambient environments
and require an inert environment to assemble supercapacitors.120
Serious research efforts are needed to unveil and mitigate this
limitation. Proper encapsulation or functionalization of
phosphorene while maintaining its electrochemical entity could
be one of the possible approaches to alleviate the stability issues.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: Jayan.Thomas@ucf.edu.
ORCID
Yeonwoong Jung: 0000-0001-6042-5551
Jayan Thomas: 0000-0003-3579-6064
Notes
The authors declare no competing financial interest.
Biographies
Kowsik Sambath Kumar is a Ph.D. student in the Materials Science and
Engineering Department at the University of Central Florida (UCF)
working under the supervision of Dr. Jayan Thomas. He received his
B.Tech in Chemical and Electrochemical Engineering from CSIR-
CECRI, India in 2016. His current research focuses on the development
of nanostructured materials for energy storage devices.
DOI: 10.1021/acsenergylett.7b01169
ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters
Nitin Choudhary is a postdoctoral researcher at the NanoScience
Technology Center (NSTC) of the University of Central Florida, USA.
He graduated from the Indian Institute of Technology (IIT), India in
the field of experimental physics/nanotechnology. He is currently
working in the field of low-dimensional materials for next-generation
electronics and energy applications.
Yeonwoong Jung is an assistant professor at the NanoScience
Technology Center (NSTC), Materials Science and Engineering, and
Electrical and Computer Engineering at the University of Central
Florida. He received his Ph.D. in materials science and engineering from
the University of Pennsylvania, Philadelphia, USA. He joined UCF in
2015 after completing his postdoctoral training at Yale University. His
research group at UCF currently focuses on developing 2D layered
materials and their hybrid systems for electronics, energy, and
environmental applications.
Jayan Thomas is an associate professor at the NanoScience Technology
Center (NSTC), College of Optics and Photonics (CREOL) and
College of Engineering and Computer Science at the University of
Central Florida. After receiving his Ph.D. from Cochin University of
Science and Technology in India, he joined the College of Optical
Sciences, the University of Arizona in 2001 as a research faculty. He
moved to UCF in 2011 and is currently working on the development of
energy harvesting devices, wearables energy devices, solar cells, and
photorefractive polymers.
■
ACKNOWLEDGMENTS
J.T. acknowledges the University of Central Florida “Reach for
the stars” award for financial support. N.C. acknowledges the
partial support from the Preeminent Postdoctoral Program (P3)
at UCF.
■
REFERENCES
(1) Yu, Z. A.; Li, C.; Abbitt, D.; Thomas, J. Flexible, sandwich-like Ag-
nanowire/PEDOT: PSS-nanopillar/MnO2 high performance super-
capacitors. J. Mater. Chem. A 2014, 2, 10923−10929.
(2) Simon, P.; Gogotsi, Y. Materials for electrochemical capacitors.
Nat. Mater. 2008, 7, 845−854.
(3) Yu, Z. N.; Duong, B.; Abbitt, D.; Thomas, J. Highly ordered MnO2
nanopillars for enhanced supercapacitor performance. Adv. Mater. 2013,
25, 3302−3306.
(4) Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D.
Challenges in the development of advanced Li-ion batteries: a review.
Energy Environ. Sci. 2011, 4, 3243−3262.
(5) Scrosati, B.; Garche, J. Lithium batteries: Status, prospects and
future. J. Power Sources 2010, 195, 2419−2430.
(6) Miller, J. R.; Simon, P. Electrochemical capacitors for energy
management. Science 2008, 321, 651−652.
(7) Yu, Z. N.; Tetard, L.; Zhai, L.; Thomas, J. Supercapacitor electrode
materials: nanostructures from 0 to 3 dimensions. Energy Environ. Sci.
2015, 8, 702−730.
(8) Choudhary, N.; Li, C.; Moore, J.; Nagaiah, N.; Zhai, L.; Jung, Y.;
Thomas, J. Asymmetric supercapacitor electrodes and devices. Adv.
Mater. 2017, 29, 1605336.
(9) Zhang, L. L.; Zhou, R.; Zhao, X. S. Graphene-based materials as
supercapacitor electrodes. J. Mater. Chem. 2010, 20, 5983−5992.
(10) Ke, Q.; Wang, J. Graphene-based materials for supercapacitor
electrodes−A review. Journal of Materiomics 2016, 2, 37−54.
(11) Lei, Z. B.; Sun, X. X.; Wang, H. J.; Liu, Z. H.; Zhao, X. S. Platelet
CMK-5 as an excellent mesoporous carbon to enhance the
pseudocapacitance of polyaniline. ACS Appl. Mater. Interfaces 2013, 5,
7501−7508.
(12) Wang, G. P.; Zhang, L.; Zhang, J. J. A review of electrode materials
for electrochemical supercapacitors. Chem. Soc. Rev. 2012, 41, 797−828.
492
Review
(13) Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. The role of
graphene for electrochemical energy storage. Nat. Mater. 2015, 14, 271−
279.
(14) Choi, W.; Choudhary, N.; Han, G. H.; Park, J.; Akinwande, D.;
Lee, Y. H. Recent development of two-dimensional transition metal
dichalcogenides and their applications. Mater. Today 2017, 20, 116−
130.
(15) Yang, Y.; Fei, H. L.; Ruan, G. D.; Xiang, C. S.; Tour, J. M. Edge-
oriented MoS2 nanoporous films as flexible electrodes for hydrogen
evolution reactions and supercapacitor devices. Adv. Mater. 2014, 26,
8163−8168.
(16) Acerce, M.; Voiry, D.; Chhowalla, M. Metallic 1T phase MoS2
nanosheets as supercapacitor electrode materials. Nat. Nanotechnol.
2015, 10, 313−318.
(17) Jiang, Y. Q.; Chen, L. Y.; Zhang, H. Q.; Zhang, Q.; Chen, W. F.;
Zhu, J. K.; Song, D. M. Two-dimensional Co3O4 thin sheets assembled
by 3D interconnected nanoflake array framework structures with
enhanced supercapacitor performance derived from coordination
complexes. Chem. Eng. J. 2016, 292, 1−12.
(18) Shi, S.; Xu, C.; Yang, C.; Chen, Y.; Liu, J.; Kang, F. Flexible
asymmetric supercapacitors based on ultrathin two-dimensional
nanosheets with outstanding electrochemical performance and aesthetic
property. Sci. Rep. 2013, 3, 1−8.
(19) Zhu, L. L.; Nuo Peh, C. K.; Zhu, T.; Lim, Y. F.; Ho, G. W.
Bifunctional 2D-on-2D MoO3 nanobelt/Ni(OH)2 nanosheets for
supercapacitor-driven electrochromic energy storage. J. Mater. Chem.
A 2017, 5, 8343−8351.
(20) Zhu, Y. Q.; Cao, C. B.; Tao, S.; Chu, W. S.; Wu, Z. Y.; Li, Y. D.
Ultrathin nickel hydroxide and oxide nanosheets: synthesis, character-
izations and excellent supercapacitor performances. Sci. Rep. 2015, 4, 1−
7.
(21) Naguib, M.; Kurtoglu, M.; Presser, V.; Lu, J.; Niu, J. J.; Heon, M.;
Hultman, L.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional nano-
crystals produced by exfoliation of Ti3AlC2. Adv. Mater. 2011, 23, 4248−
4253.
(22) Park, C. M.; Kim, J. H.; Kim, H.; Sohn, H. J. Li-alloy based anode
materials for Li secondary batteries. Chem. Soc. Rev. 2010, 39, 3115−
3141.
(23) Choudhary, N.; Li, C.; Chung, H. S.; Moore, J.; Thomas, J.; Jung,
Y. High-performance one-body core/shell nanowire supercapacitor
enabled by conformal growth of capacitive 2D WS2 layers. ACS Nano
2016, 10, 10726−10735.
(24) Zhu, J. X.; Sun, W. P.; Yang, D.; Zhang, Y.; Hoon, H. H.; Zhang,
H.; Yan, Q. Y. Multifunctional architectures constructing of PANI
nanoneedle arrays on MoS2 thin nanosheets for high-energy super-
capacitors. Small 2015, 11, 4123−4129.
(25) Nagaraju, D. H.; Wang, Q. X.; Beaujuge, P.; Alshareef, H. N. Two-
dimensional heterostructures of V2O5 and reduced graphene oxide as
electrodes for high energy density asymmetric supercapacitors. J. Mater.
Chem. A 2014, 2, 17146−17152.
(26) Fan, Z. J.; Yan, J.; Wei, T.; Zhi, L. J.; Ning, G. Q.; Li, T. Y.; Wei, F.
Asymmetric supercapacitors based on graphene/MnO2 and activated
carbon nanofiber electrodes with high power and energy density. Adv.
Funct. Mater. 2011, 21, 2366−2375.
(27) Yan, J.; Fan, Z. J.; Sun, W.; Ning, G. Q.; Wei, T.; Zhang, Q.; Zhang,
R. F.; Zhi, L. J.; Wei, F. Advanced ssymmetric supercapacitors based on
Ni(OH)2/graphene and porous graphene electrodes with high energy
density. Adv. Funct. Mater. 2012, 22, 2632−2641.
(28) Cao, L. J.; Yang, S. B.; Gao, W.; Liu, Z.; Gong, Y. J.; Ma, L. L.; Shi,
G.; Lei, S. D.; Zhang, Y. H.; Zhang, S. T.; Vajtai, R.; Ajayan, P. M. Direct
laser-patterned micro-supercapacitors from paintable MoS2 films. Small
2013, 9, 2905−2910.
(29) Muller, G. A.; Cook, J. B.; Kim, H. S.; Tolbert, S. H.; Dunn, B.
High performance pseudocapacitor based on 2D layered metal
chalcogenide nanocrystals. Nano Lett. 2015, 15, 1911−1917.
(30) Koroteev, V. O.; Kuznetsova, I. V.; Kurenya, A. G.; Kanygin, M.
A.; Fedorovskaya, E. O.; Mikhlin, Y. L.; Chuvilin, A. L.; Bulusheva, L. G.;
Okotrub, A. V. Enhanced supercapacitance of vertically aligned multi-
DOI: 10.1021/acsenergylett.7b01169
ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters
wall carbon nanotube array covered by MoS2 nanoparticles. Phys. Status
Solidi B 2016, 253, 2451−2456.
(31) Choudhary, N.; Patel, M.; Ho, Y. H.; Dahotre, N. B.; Lee, W.;
Hwang, J. Y.; Choi, W. Directly deposited MoS2 thin film electrodes for
high performance supercapacitors. J. Mater. Chem. A 2015, 3, 24049−
24054.
(32) Soon, J. M.; Loh, K. P. Electrochemical double-layer capacitance
of MoS2 nanowall films. Electrochem. Solid-State Lett. 2007, 10, A250−
A254.
(33) Zhang, F.; Tang, Y. B.; Liu, H.; Ji, H. Y.; Jiang, C. L.; Zhang, J.;
Zhang, X. L.; Lee, C. S. Uniform incorporation of flocculent
molybdenum disulfide nanostructure into three-dimensional porous
graphene as an anode for high-performance lithium ion batteries and
hybrid supercapacitors. ACS Appl. Mater. Interfaces 2016, 8, 4691−4699.
(34) Ge, Y.; Jalili, R.; Wang, C.; Zheng, T.; Chao, Y.; Wallace, G. G. A
robust free-standing MoS2/poly (3, 4-ethylenedioxythiophene): poly
(styrenesulfonate) film for supercapacitor applications. Electrochim. Acta
2017, 235, 348−355.
(35) Yang, M.; Jeong, J. M.; Huh, Y. S.; Choi, B. G. High-performance
supercapacitor based on three-dimensional MoS2/graphene aerogel
composites. Compos. Sci. Technol. 2015, 121, 123−128.
(36) Yang, C.; Chen, Z. X.; Shakir, I.; Xu, Y. X.; Lu, H. B. Rational
synthesis of carbon shell coated polyaniline/MoS2 monolayer
composites for high-performance supercapacitors. Nano Res. 2016, 9,
951−962.
(37) Bissett, M. A.; Kinloch, I. A.; Dryfe, R. A. W. Characterization of
MoS2-graphene composites for high-performance coin cell super-
capacitors. ACS Appl. Mater. Interfaces 2015, 7, 17388−17398.
(38) Patil, S.; Harle, A.; Sathaye, S.; Patil, K. Development of a novel
method to grow mono-/few-layered MoS2 films and MoS2-graphene
hybrid films for supercapacitor applications. CrystEngComm 2014, 16,
10845−10855.
(39) Huang, K. J.; Wang, L.; Liu, Y. J.; Liu, Y. M.; Wang, H. B.; Gan, T.;
Wang, L. L. Layered MoS2-graphene composites for supercapacitor
applications with enhanced capacitive performance. Int. J. Hydrogen
Energy 2013, 38, 14027−14034.
(40) Wang, J.; Wu, Z. C.; Hu, K. H.; Chen, X. Y.; Yin, H. B. High
conductivity graphene-like MoS2/polyaniline nanocomposites and its
application in supercapacitor. J. Alloys Compd. 2015, 619, 38−43.
(41) Ma, G. F.; Peng, H.; Mu, J. J.; Huang, H. H.; Zhou, X. Z.; Lei, Z. Q.
In situ intercalative polymerization of pyrrole in graphene analogue of
MoS2 as advanced electrode material in supercapacitor. J. Power Sources
2013, 229, 72−78.
(42) Wang, J.; Wu, Z. C.; Yin, H. B.; Li, W.; Jiang, Y. Poly(3,4-
ethylenedioxythiophene)/MoS2 nanocomposites with enhanced elec-
trochemical capacitance performance. RSC Adv. 2014, 4, 56926−56932.
(43) Feng, J.; Sun, X.; Wu, C. Z.; Peng, L. L.; Lin, C. W.; Hu, S. L.;
Yang, J. L.; Xie, Y. Metallic few-layered VS2 ultrathin nanosheets: high
two-dimensional conductivity for in-plane supercapacitors. J. Am. Chem.
Soc. 2011, 133, 17832−17838.
(44) Khalil, A.; Liu, Q.; He, Q.; Xiang, T.; Liu, D.; Wang, C.; Fang, Q.;
Song, L. Metallic 1T-WS2 nanoribbons as highly conductive electrodes
for supercapacitors. RSC Adv. 2016, 6, 48788−48791.
(45) Yang, X.; Niu, H.; Jiang, H.; Wang, Q.; Qu, F. A high energy
density all-solid-state asymmetric supercapacitor based on MoS2/
graphene nanosheets and MnO2/graphene hybrid electrodes. J. Mater.
Chem. A 2016, 4, 11264−11275.
(46) da Silveira Firmiano, E. G.; Rabelo, A. C.; Dalmaschio, C. J.;
Pinheiro, A. N.; Pereira, E. C.; Schreiner, W. H.; Leite, E. R.
Supercapacitor electrodes obtained by directly bonding 2D MoS2 on
reduced graphene oxide. Adv. Energy Mater. 2014, 4, 1301380.
(47) Huang, K. J.; Wang, L.; Zhang, J. Z.; Wang, L. L.; Mo, Y. P. One-
step preparation of layered molybdenum disulfide/multi-walled carbon
nanotube composites for enhanced performance supercapacitor. Energy
2014, 67, 234−240.
(48) Sun, G. Z.; Zhang, X.; Lin, R. Z.; Yang, J.; Zhang, H.; Chen, P.
Hybrid fibers made of molybdenum disulfide, reduced graphene oxide,
and multi-walled carbon nanotubes for solid-state, flexible, asymmetric
supercapacitors. Angew. Chem., Int. Ed. 2015, 54, 4651−4656.
493
Review
(49) Yang, X.; Niu, H.; Jiang, H.; Wang, Q.; Qu, F. Y. A high energy
density all-solid-state asymmetric supercapacitor based on MoS2/
graphene nanosheets and MnO2/graphene hybrid electrodes. J. Mater.
Chem. A 2016, 4, 11264−11275.
(50) Kim, J.; Lee, J.; You, J.; Park, M. S.; Al Hossain, M. S.; Yamauchi,
Y.; Kim, J. H. Conductive polymers for next-generation energy storage
systems: recent progress and new functions. Mater. Horiz. 2016, 3, 517−
535.
(51) Shown, I.; Ganguly, A.; Chen, L. C.; Chen, K. H. Conducting
polymer-based flexible supercapacitor. Energy Sci. Eng. 2015, 3, 2−26.
(52) Ren, L. J.; Zhang, G. N.; Yan, Z.; Kang, L. P.; Xu, H.; Shi, F.; Lei, Z.
B.; Liu, Z. H. Three-dimensional tubular MoS2/PANI hybrid electrode
for high rate performance supercapacitor. ACS Appl. Mater. Interfaces
2015, 7, 28294−28302.
(53) Wang, X.; Kalali, E. N.; Wang, D. Y. An in situ polymerization
approach for functionalized MoS2/nylon-6 nanocomposites with
enhanced mechanical properties and thermal stability. J. Mater. Chem.
A 2015, 3, 24112−24120.
(54) Huang, K. J.; Wang, L.; Liu, Y. J.; Wang, H. B.; Liu, Y. M.; Wang, L.
L. Synthesis of polyaniline/2-dimensional graphene analog MoS2
composites for high-performance supercapacitor. Electrochim. Acta
2013, 109, 587−594.
(55) Wang, D.-W.; Li, F.; Cheng, H.-M. Hierarchical porous nickel
oxide and carbon as electrode materials for asymmetric supercapacitor. J.
Power Sources 2008, 185, 1563−1568.
(56) Wei, W.; Cui, X.; Chen, W.; Ivey, D. G. Manganese oxide-based
materials as electrochemical supercapacitor electrodes. Chem. Soc. Rev.
2011, 40, 1697−1721.
(57) Subramani, K.; Kowsik, S.; Sathish, M. Facile and scalable ultra−
fine cobalt oxide/reduced graphene oxide nanocomposites for high
energy asymmetric supercapacitors. Chemistryselect 2016, 1, 3455−
3467.
(58) Guan, C.; Liu, J.; Wang, Y.; Mao, L.; Fan, Z.; Shen, Z.; Zhang, H.;
Wang, J. Iron oxide-decorated carbon for supercapacitor anodes with
ultrahigh energy density and outstanding cycling stability. ACS Nano
2015, 9, 5198−5207.
(59) Jang, J. H.; Kato, A.; Machida, K.; Naoi, K. Supercapacitor
performance of hydrous ruthenium oxide electrodes prepared by
electrophoretic deposition. J. Electrochem. Soc. 2006, 153, A321−A328.
(60) Giardi, R.; Porro, S.; Topuria, T.; Thompson, L.; Pirri, C. F.; Kim,
H.-C. One-pot synthesis of graphene-molybdenum oxide hybrids and
their application to supercapacitor electrodes. Applied Materials Today
2015, 1, 27−32.
(61) Pan, X. X.; Chen, X. M.; Li, Y.; Yu, Z. N. Facile synthesis of Co3O4
nanosheets electrode with ultrahigh specific capacitance for electro-
chemical supercapacitors. Electrochim. Acta 2015, 182, 1101−1106.
(62) Yuan, C. Z.; Zhang, X. G.; Su, L. H.; Gao, B.; Shen, L. F. Facile
synthesis and self-assembly of hierarchical porous NiO nano/micro
spherical superstructures for high performance supercapacitors. J. Mater.
Chem. 2009, 19, 5772−5777.
(63) Peng, L. L.; Peng, X.; Liu, B. R.; Wu, C. Z.; Xie, Y.; Yu, G. H.
Ultrathin two-dimensional MnO2/graphene hybrid nanostructures for
high-performance, flexible planar supercapacitors. Nano Lett. 2013, 13,
2151−2157.
(64) Zhi, J.; Yang, C.; Lin, T.; Cui, H.; Wang, Z.; Zhang, H.; Huang, F.
Flexible all solid state supercapacitor with high energy density
employing black titania nanoparticles as a conductive agent. Nanoscale
2016, 8, 4054−4062.
(65) Chen, P. C.; Shen, G. Z.; Shi, Y.; Chen, H. T.; Zhou, C. W.
Preparation and characterization of flexible asymmetric supercapacitors
based on transition-metal-oxide nanowire/single-walled carbon nano-
tube hybrid thin-film electrodes. ACS Nano 2010, 4, 4403−4411.
(66) He, Y.; Chen, W.; Li, X.; Zhang, Z.; Fu, J.; Zhao, C.; Xie, E.
Freestanding three-dimensional graphene/MnO2 composite networks
as ultralight and flexible supercapacitor electrodes. ACS Nano 2013, 7,
174−182.
(67) Ma, Z.; Shao, G.; Fan, Y.; Wang, G.; Song, J.; Shen, D.
Construction of hierarchical α-MnO2 nanowires@ ultrathin δ-MnO2
nanosheets core−shell nanostructure with excellent cycling stability for
DOI: 10.1021/acsenergylett.7b01169
ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters
High-Power Asymmetric Supercapacitor Electrodes. ACS Appl. Mater.
Interfaces 2016, 8, 9050−9058.
(68) Jiang, J. H.; Kucernak, A. Electrochemical supercapacitor material
based on manganese oxide: preparation and characterization. Electro-
chim. Acta 2002, 47, 2381−2386.
(69) Gao, P.; Metz, P.; Hey, T.; Gong, Y.; Liu, D.; Edwards, D. D.;
Howe, J. Y.; Huang, R.; Misture, S. T. The critical role of point defects in
improving the specific capacitance of δ-MnO2 nanosheets. Nat.
Commun. 2017, 8, 14559.
(70) Qin, J.; Wu, Z.-S.; Zhou, F.; Dong, Y.; Xiao, H.; Zheng, S.; Wang,
S.; Shi, X.; Huang, H.; Sun, C.; et al. Simplified fabrication of high areal
capacitance all-solid-state micro-supercapacitors based on graphene and
MnO2 nanosheets. Chin. Chem. Lett. 2017, 1−5.
(71) Xia, H.; Wang, Y.; Lin, J. Y.; Lu, L. Hydrothermal synthesis of
MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath
hierarchy architecture for supercapacitors. Nanoscale Res. Lett. 2012, 7,
33.
(72) Mondal, A. K.; Wang, B.; Su, D. W.; Wang, Y.; Chen, S. Q.; Zhang,
X. G.; Wang, G. X. Graphene/MnO2 hybrid nanosheets as high
performance electrode materials for supercapacitors. Mater. Chem. Phys.
2014, 143, 740−746.
(73) Mendoza-Sanchez, B.; Coelho, J.; Pokle, A.; Nicolosi, V. A 2D
graphene-manganese oxide nanosheet hybrid synthesized by a single
step liquid-phase co-exfoliation method for supercapacitor applications.
Electrochim. Acta 2015, 174, 696−705.
(74) Liu, D. Q.; Wang, X.; Wang, X. B.; Tian, W.; Liu, J. W.; Zhi, C. Y.;
He, D. Y.; Bando, Y.; Golberg, D. Ultrathin nanoporous Fe3O4-carbon
nanosheets with enhanced supercapacitor performance. J. Mater. Chem.
A 2013, 1, 1952−1955.
(75) Qu, Q. T.; Yang, S. B.; Feng, X. L. 2D sandwich-like sheets of iron
oxide grown on graphene as high energy anode material for
supercapacitors. Adv. Mater. 2011, 23, 5574−5580.
(76) Yang, Q.; Lu, Z. Y.; Sun, X. M.; Liu, J. F. Ultrathin Co3O4
nanosheet arrays with high supercapacitive performance. Sci. Rep. 2013,
3, 1−7.
(77) Lee, K. K.; Chin, W. S.; Sow, C. H. Cobalt-based compounds and
composites as electrode materials for high-performance electrochemical
capacitors. J. Mater. Chem. A 2014, 2, 17212−17248.
(78) Jiang, Y.; Chen, L.; Zhang, H.; Zhang, Q.; Chen, W.; Zhu, J.; Song,
D. Two-dimensional Co3O4 thin sheets assembled by 3D intercon-
nected nanoflake array framework structures with enhanced super-
capacitor performance derived from coordination complexes. Chem.
Eng. J. 2016, 292, 1−12.
(79) Yuan, C. Z.; Yang, L.; Hou, L. R.; Shen, L. F.; Zhang, X. G.; Lou, X.
W. Growth of ultrathin mesoporous Co3O4 nanosheet arrays on Ni
foam for high-performance electrochemical capacitors. Energy Environ.
Sci. 2012, 5, 7883−7887.
(80) Yu, W.; Jiang, X.; Ding, S.; Li, B. Q. Preparation and
electrochemical characteristics of porous hollow spheres of NiO
nanosheets as electrodes of supercapacitors. J. Power Sources 2014,
256, 440−448.
(81) Gao, Z.; Yang, W. L.; Yan, Y. X.; Wang, J.; Ma, J.; Zhang, X. M.;
Xing, B. H.; Liu, L. H. Synthesis and exfoliation of layered α-Co(OH)2
nanosheets and their electrochemical performance for supercapacitors.
Eur. J. Inorg. Chem. 2013, 2013, 4832−4838.
(82) Tang, J.; Liu, D. Q.; Zheng, Y. X.; Li, X. W.; Wang, X. H.; He, D. Y.
Effect of Zn-substitution on cycling performance of α -Co(OH)2
nanosheet electrode for supercapacitors. J. Mater. Chem. A 2014, 2,
2585−2591.
(83) Lu, Z. Y.; Chang, Z.; Zhu, W.; Sun, X. M. β-phased Ni(OH)2
nanowall film with reversible capacitance higher than theoretical Faradic
capacitance. Chem. Commun. 2011, 47, 9651−9653.
(84) Sun, W. P.; Rui, X. H.; Ulaganathan, M.; Madhavi, S.; Yan, Q. Y.
Few-layered Ni(OH)2 nanosheets for high-performance supercapaci-
tors. J. Power Sources 2015, 295, 323−328.
(85) Jiang, H.; Zhao, T.; Li, C. Z.; Ma, J. Hierarchical self-assembly of
ultrathin nickel hydroxide nanoflakes for high-performance super-
capacitors. J. Mater. Chem. 2011, 21, 3818−3823.
494
Review
(86) Zhao, T.; Jiang, H.; Ma, J. Surfactant-assisted electrochemical
deposition of α-cobalt hydroxide for supercapacitors. J. Power Sources
2011, 196, 860−864.
(87) Zhang, J.; Wang, X. C.; Ma, J.; Liu, S.; Yi, X. B. Preparation of
cobalt hydroxide nanosheets on carbon nanotubes/carbon paper
conductive substrate for supercapacitor application. Electrochim. Acta
2013, 104, 110−116.
(88) Huang, J. C.; Xu, P. P.; Cao, D. X.; Zhou, X. B.; Yang, S. N.; Li, Y.
J.; Wang, G. L. Asymmetric supercapacitors based on β-Ni(OH)2
nanosheets and activated carbon with high energy density. J. Power
Sources 2014, 246, 371−376.
(89) Wang, R. T.; Yan, X. B.; Lang, J. W.; Zheng, Z. M.; Zhang, P. A
hybrid supercapacitor based on flower-like Co(OH)(2) and urchin-like
VN electrode materials. J. Mater. Chem. A 2014, 2, 12724−12732.
(90) Gao, S.; Sun, Y. F.; Lei, F. C.; Liang, L.; Liu, J. W.; Bi, W. T.; Pan,
B. C.; Xie, Y. Ultrahigh energy density realized by a single-layer β-
Co(OH)2 all-solid-state asymmetric supercapacitor. Angew. Chem., Int.
Ed. 2014, 53, 12789−12793.
(91) Wang, H. L.; Casalongue, H. S.; Liang, Y. Y.; Dai, H. J. Ni(OH)2
Nanoplates grown on graphene as advanced electrochemical
pseudocapacitor materials. J. Am. Chem. Soc. 2010, 132, 7472−7477.
(92) Li, R.; Hu, Z.; Shao, X.; Cheng, P.; Li, S.; Yu, W.; Lin, W.; Yuan, D.
Large scale synthesis of NiCo layered double hydroxides for superior
asymmetric electrochemical capacitor. Sci. Rep. 2016, 6 (18737), 1−9.
(93) Nguyen, T.; Boudard, M.; Carmezim, M. J.; Montemor, M. F.
Layered Ni(OH)2-Co(OH)2 films prepared by electrodeposition as
charge storage electrodes for hybrid supercapacitors. Sci. Rep. 2017, 7,
39980.
(94) Chen, H.; Hu, L. F.; Yan, Y.; Che, R. C.; Chen, M.; Wu, L. M. One-
step fabrication of ultrathin porous nickel hydroxide-manganese dioxide
hybrid nanosheets for supercapacitor electrodes with excellent
capacitive performance. Adv. Energy Mater. 2013, 3, 1636−1646.
(95) Anasori, B.; Xie, Y.; Beidaghi, M.; Lu, J.; Hosler, B. C.; Hultman,
L.; Kent, P. R. C.; Gogotsi, Y.; Barsoum, M. W. Two-dimensional,
ordered, double transition metals carbides (MXenes). ACS Nano 2015,
9, 9507−9516.
(96) Kurtoglu, M.; Naguib, M.; Gogotsi, Y.; Barsoum, M. W. First
principles study of two-dimensional early transition metal carbides. MRS
Commun. 2012, 2, 133−137.
(97) Lei, J. C.; Zhang, X.; Zhou, Z. Recent advances in MXene:
preparation, properties, and applications. Front Phys-Beijing 2015, 10,
276−286.
(98) Lukatskaya, M. R.; Mashtalir, O.; Ren, C. E.; Dall’Agnese, Y.;
Rozier, P.; Taberna, P. L.; Naguib, M.; Simon, P.; Barsoum, M. W.;
Gogotsi, Y. Cation intercalation and high volumetric capacitance of two-
dimensional titanium carbide. Science 2013, 341, 1502−1505.
(99) Ghidiu, M.; Lukatskaya, M. R.; Zhao, M. Q.; Gogotsi, Y.;
Barsoum, M. W. Conductive two-dimensional titanium carbide ’clay’
with high volumetric capacitance. Nature 2014, 516, 78−81.
(100) Hu, M. M.; Li, Z. J.; Zhang, H.; Hu, T.; Zhang, C.; Wu, Z.; Wang,
X. H. Self-assembled Ti3C2Tx MXene film with high gravimetric
capacitance. Chem. Commun. 2015, 51, 13531−13533.
(101) Dall’Agnese, Y.; Lukatskaya, M. R.; Cook, K. M.; Taberna, P. L.;
Gogotsi, Y.; Simon, P. High capacitance of surface-modified 2D titanium
carbide in acidic electrolyte. Electrochem. Commun. 2014, 48, 118−122.
(102) Lin, S. Y.; Zhang, X. T. Two-dimensional titanium carbide
electrode with large mass loading for supercapacitor. J. Power Sources
2015, 294, 354−359.
(103) Krishnamoorthy, K.; Pazhamalai, P.; Sahoo, S.; Kim, S. J.
Titanium carbide sheet based high performance wire type solid state
supercapacitors. J. Mater. Chem. A 2017, 5, 5726−5736.
(104) Hu, H. B.; Hua, T. An easily manipulated protocol for patterning
of MXenes on paper for planar micro-supercapacitors. J. Mater. Chem. A
2017, 5, 19639−19648.
(105) Li, H. Y.; Hou, Y.; Wang, F. X.; Lohe, M. R.; Zhuang, X. D.; Niu,
L.; Feng, X. L. Flexible all-solid-state supercapacitors with high
volumetric capacitances boosted by solution processable MXene and
electrochemically exfoliated graphene. Adv. Energy Mater. 2017, 7,
1601847.
DOI: 10.1021/acsenergylett.7b01169
ACS Energy Lett. 2018, 3, 482−495
ACS Energy Letters Review

(106) Peng, Y. Y.; Akuzum, B.; Kurra, N.; Zhao, M. Q.; Alhabeb, M.;
Anasori, B.; Kumbur, E. C.; Alshareef, H. N.; Ger, M. D.; Gogotsi, Y. All-
MXene (2D titanium carbide) solid-state microsupercapacitors for on-
chip energy storage. Energy Environ. Sci. 2016, 9, 2847−2854.
(107) Hu, M.; Li, Z.; Li, G.; Hu, T.; Zhang, C.; Wang, X. All-solid-state
flexible fiber-based MXene supercapacitors. Advanced Materials
Technologies 2017, 2, 1700143.
(108) Zhu, J. F.; Tang, Y.; Yang, C. H.; Wang, F.; Cao, M. J.
Composites of TiO2 nanoparticles deposited on Ti3C2 MXene
nanosheets with enhanced electrochemical performance. J. Electrochem.
Soc. 2016, 163, A785−A791.
(109) Boota, M.; Anasori, B.; Voigt, C.; Zhao, M. Q.; Barsoum, M. W.;
Gogotsi, Y. Pseudocapacitive electrodes produced by oxidant-free
polymerization of pyrrole between the layers of 2D titanium carbide
(MXene). Adv. Mater. 2016, 28, 1517−1522.
(110) Zhao, C. J.; Wang, Q.; Zhang, H.; Passerini, S.; Qian, X. Z. Two-
dimensional titanium carbide/RGO composite for high-performance
supercapacitors. ACS Appl. Mater. Interfaces 2016, 8, 15661−15667.
(111) Dall’Agnese, Y.; Rozier, P.; Taberna, P. L.; Gogotsi, Y.; Simon, P.
Capacitance of two-dimensional titanium carbide (MXene) and
MXene/carbon nanotube composites in organic electrolytes. J. Power
Sources 2016, 306, 510−515.
(112) Zhu, J. F.; Lu, X.; Wang, L. Synthesis of a MoO3/Ti3C2Tx
composite with enhanced capacitive performance for supercapacitors.
RSC Adv. 2016, 6, 98506−98513.
(113) Ling, Z.; Ren, C. E.; Zhao, M. Q.; Yang, J.; Giammarco, J. M.;
Qiu, J. S.; Barsoum, M. W.; Gogotsi, Y. Flexible and conductive MXene
films and nanocomposites with high capacitance. Proc. Natl. Acad. Sci. U.
S. A. 2014, 111, 16676−16681.
(114) Zhao, M. Q.; Ren, C. E.; Ling, Z.; Lukatskaya, M. R.; Zhang, C.
F.; Van Aken, K. L.; Barsoum, M. W.; Gogotsi, Y. Flexible MXene/
carbon nanotube composite paper with high volumetric capacitance.
Adv. Mater. 2015, 27, 339−345.
(115) Rakhi, R. B.; Ahmed, B.; Anjum, D.; Alshareef, H. N. Direct
chemical synthesis of MnO2 nanowhiskers on transition metal carbide
surfaces for supercapacitor applications. ACS Appl. Mater. Interfaces
2016, 8, 18806−18814.
(116) Castellanos-Gomez, A.; Vicarelli, L.; Prada, E.; Island, J. O.;
Narasimha-Acharya, K. L.; Blanter, S. I.; Groenendijk, D. J.; Buscema,
M.; Steele, G. A.; Alvarez, J. V.; Zandbergen, H. W.; Palacios, J. J.; van der
Zant, H. S. J. Isolation and characterization of few-layer black
phosphorus. 2D Mater. 2014, 1, 025001.
(117) Hao, C. X.; Yang, B. C.; Wen, F. S.; Xiang, J. Y.; Li, L.; Wang, W.
H.; Zeng, Z. M.; Xu, B.; Zhao, Z. S.; Liu, Z. Y.; Tian, Y. J. Flexible all-
solid-state supercapacitors based on liquid-exfoliated black-phosphorus
nanoflakes. Adv. Mater. 2016, 28, 3194−3201.
(118) Chen, X. H.; Xu, G. G.; Ren, X. H.; Li, Z. J.; Qi, X.; Huang, K.;
Zhang, H.; Huang, Z. Y.; Zhong, J. X. A black/red phosphorus hybrid as
an electrode material for high-performance Li-ion batteries and
supercapacitors. J. Mater. Chem. A 2017, 5, 6581−6588.
(119) Xiao, H.; Wu, Z.-S.; Chen, L.; Zhou, F.; Zheng, S.; Ren, W.;
Cheng, H.-M.; Bao, X. One-step device fabrication of phosphorene and
graphene interdigital micro-supercapacitors with high energy density.
ACS Nano 2017, 11, 7284−7292.
(120) Pei, J. J.; Gai, X.; Yang, J.; Wang, X. B.; Yu, Z. F.; Choi, D. Y.;
Luther-Davies, B.; Lu, Y. R. Producing air-stable monolayers of
phosphorene and their defect engineering. Nat. Commun. 2016, 7,
10450.

495 DOI: 10.1021/acsenergylett.7b01169

ACS Energy Lett. 2018, 3, 482−495