Materials Research Express

TOPICAL REVIEW • OPEN ACCESS

Recent citations
A review on MXene for energy storage application: - MXene for high energy and power density:
effect of interlayer distance a perspective
Chengxiang Wang et al

- Printing and coating MXenes for

To cite this article: Ruby Garg et al 2020 Mater. Res. Express 7 022001 electrochemical energy storage devices
Sina Abdolhosseinzadeh et al

- A Freeze-and-Thaw-Assisted Approach to
Fabricate MXene/ZIF-8 Composites for
High-Performance Supercapacitors and
View the article online for updates and enhancements. Methylene Blue Adsorption
Yue Li et al

This content was downloaded from IP address 201.141.214.47 on 07/12/2020 at 03:40

 Mater. Res. Express 7 (2020) 022001 https://doi.org/10.1088/2053-1591/ab750d

TOPICAL REVIEW

A review on MXene for energy storage application: effect of interlayer

OPEN ACCESS
distance
RECEIVED
17 October 2019
Ruby Garg, Alpana Agarwal and Mohit Agarwal
REVISED
10 January 2020
Department of Electronics and Communication Engineering, Thapar Institute of Engineering & Technology, Patiala, Punjab 147004, India

ACCEPTED FOR PUBLICATION

E-mail: mohit.agarwal@thapar.edu
11 February 2020
Keywords: supercapacitor, MXene, MAX, battery, intercalation
PUBLISHED
24 February 2020

Original content from this Abstract

work may be used under
the terms of the Creative
To meet the energy needs batteries and supercapacitors are evolved as a promising candidate from the
Commons Attribution 4.0 class of energy storage devices. The growth in the development of new 2D electrode materials brings a
licence.
new revolution in energy storage devices with a comprehensive investigation. MXene, a new family of
Any further distribution of
this work must maintain 2D metal carbides, nitrides and carbonitrides due to their attractive electrical and electrochemical
attribution to the
author(s) and the title of properties e.g. hydrophilicity, conductivity, surface area, topological structure have gained huge
the work, journal citation
and DOI.
attention. In this review, we discussed different MXene synthesis routes using different etchants e.g.
hydrofluoric acid, ammonium hydrazine, lithium fluoride, and hydrochloric acid, etc showing that
fluorine formation is compulsory to etch the aluminum layer from its precursor. Due to the advantage
of large interlayer spacing between the MXene layers in MXene, the effect of intercalation on the
performance of batteries and supercapacitors using MXene as electrodes by various sized cations are
reviewed. Different MXene hybrids as supercapacitor electrodes will also be summarized. Lastly, the
conclusion and future scope of MXene to be done in various supercapacitor applications are also
presented.

1. Introduction

The risk of energy crisis for the new generation depends on our production, storage, and utilization of the
currently available fuels to produce energy [1]. Moreover, the continuous growth in the population increasing
day by day and thus the energy crisis is again becoming a major concern. In this era, life without mobile phones,
laptops, cameras, etc is incomprehensible thus leading to high energy consumption. Continuous depletion of
energy resources demands a suitable, energy-efficient and environment-friendly energy storage device.
Currently, a variety of energy storage devices are available e.g. batteries [2], capacitors [3] and supercapacitors [4]
to overcome the above problems. But the outcomes of all these devices depend on efficiency, cost, and stability of
the electrode materials that are being used in these devices. Though a large number of noble metals e.g. Pt, Ru, Ir
as an electrode has been used for storing the energy to fulfill the energy requirements due to limitations such as
high cost and less availability of these metals reduces their use in practical day to day needs [5–11]. Hence, a
number of noble non-metals [12–15] are presented but their performance is poor as compared to the noble
metals. Therefore, the major research area in this field is to find the efficient fabrication methods or evolution of
new electrode materials that can help in achieving the future energy requirements [16]. A large number of
carbon derivatives [4], metal oxides and conducting polymers are used as an supercapacitor electrodes e.g.
activated carbon [17], carbon nanotubes [18], carbon aerogels [19], graphene [20], ruthenium dioxide [21],
magnesium oxide [22], polypropylene, polyaniline and poly-ethyl dioxythiophene [23] etc. The activated carbon
was successfully used in supercapacitor as electrode material in the year 2006 due to its large number of
advantages like large specific surface area (up to 3000 m2 g−1), abundance, simple production method. It can be
prepared from both the natural (coal, wood, coconut shell) and chemical precursor [17]. However, the
capacitance results obtained whereas very limited due to the presence of various pore size distributions [24] as
during the activation process of activated carbon, the controllability in the formation of micro, meso, and

© 2020 The Author(s). Published by IOP Publishing Ltd

Mater. Res. Express 7 (2020) 022001 R Garg et al

macropores is very limited [17]. The carbon nanotubes and graphene were also studied in the literature [4]. It is
observed from the previous studies that the graphene structure poses a serious limitation on device capacitance
as the graphene layers get agglomerated easily and thus the electrode area is not accessible completely by the
electrolyte ions [25]. Further, to increase the supercapacitor capacitance Conway et al used ruthenium oxide
(RuO2) as electrode material in the device [23]. However, the cost of RuO2 is very high which opens new doors
for other metal oxide materials. The magnesium oxide (MnO2) can be a good alternative to ruthenium oxide
because of its low-cost but used very limited in the literature due to low conductivity (10−4–10−5 S cm−1) and
thus requires extra attention to enhance the conductivity [26].
New electrode materials are getting researched day by day by various authors to find a unique solution for
energy storage devices. In this context, the main focus is going towards the 2D materials due to their excellent
physical and chemical properties as compared to their properties in the bulk [27]. During this investigation,
various new members of 2D materials like metal-organic frameworks (MoF) [28, 29], polyoxometalates (POM)
[30] and black phosphorus (BP) [31] are discovered. The major drawbacks of these 2D electrode materials
include poor specific capacitance, less electrical conductivity, structure degradation and limited transport of the
ions/electrons. The serious obstacle in many of these electrode materials includes expansion in the volume, less
interlayer spacing, less conductivity, and hydrophobic nature. Moreover, the surface oxidation and surface
defects limit their scope for energy storage applications [32]. In 2011 Naguib et al [33] showed the potential
application of MXene as electrode material in supercapacitor with remarkable device performance. However,
MXene [32–34], a new member of the 2D family is unique in the way that it has large interlayer spacing, excellent
electrical conductivity, fast diffusion of ions and molecules, easily accessible structure, good thermal stability,
hydrophilic nature, thickness controllability, and large surface area. However, the problem of restacking in
MXene sheets can be easily avoided by including various spacers between the MXene layers. In viewing the above
fact, the MXene seems to be the most promising candidate as an electrode material because the separation
between MXene layers can be controlled systematically [35]. This aspect of the MXene is highly under research
and required a comprehensive list of the work done in this area. Hence, on the MXene materials, a highly focused
review is needed to be discussed for their development as emerging electrode material in energy storage
applications. This review addresses the latest trend of MXene synthesis using various etchants such as
hydrofluoric acid, hydrazine, lithium fluoride and hydrochloric acid. Also, the effect of intercalating cations on
the MXene interlayer distance in various energy storage devices is reviewed. Finally, an outlook on future scope
of MXene as an electrode material in supercapacitor related applications will be discussed.

2. Synthetic approaches for preparing 2D MXene from MAX precursor

MXene belongs to the family of 2D layered transition metal carbides, nitrides or carbonitrides. It is evolved as
promising electrode material in energy storage and conversion devices because of its excellent properties. The
precursor material for MXene preparation includes titanium aluminum carbide (Ti3AlC2) [36] which is
prepared from the ‘pressure less calcination’ of titanium, aluminum, graphite. The raw material such as Ti
(<40 μm powder size, 99% purity), Al (<40 μm powder size, 99% purity) and graphite powders (<5 μm
powder size, 99% purity) can be taken as a starting material in the proportion of 3:1:2 and mixed in ethanol
solution under 20MPa pressure. The single-phase precursor can be obtained after calcining at 1400 °C for 4 h.
The reactions that occurred during the formation of ternary carbide are shown above. The ternary carbide
shows both the combinative properties of ceramics and metals. It resembles the metals in the way that it is
thermally and electrically conductive, shock resistance. Like ceramics, it is lightweight, stiff, thermally stable and
retained its properties even at high temperatures. Hence, it is considered as an attractive material for various
applications. The ternary carbide is synthesized by various researchers by various techniques [37–39]. But all
these techniques include various intermediate quite stable binary and ternary phases like TiC, Al3Ti, Al2Ti, AlTi,
etc [36].
Earlier people were used gaseous halides in vacuum to etch the A atomic layer from MAX precursor [40–42]
while using these gaseous halides there are some serious limitations that it produced different structures (i.e. 3D
in spite of 2D) of carbon and carbides because of etching of both ‘M’ and ‘A’ elements from the MAX precursor.
Hence, the preparation of MXene is carried out from the formula Mn+1AXn (MAX), where ‘M’ belongs to the
family of early transition metals such as scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), etc ‘A’ is an
element belonging to the 12–16 group elements such as cadmium (Cd), aluminum (Al), silicon (Si), phosphorus
(P), etc and ‘X’ can be carbon, nitrogen, carbon, and nitrogen [43–46]. The MXene also known as sheets of
transition metal with exposed surface is prepared by removing ‘A’ elements selectively from MAX precursor
using HF or NH4HF2 as shown in equations (1) and (4) Though the bond between M and A is metallic and strong
but it is replaced by hydrogen bonds which are weaker such as hydroxyl OH, oxygen O, and fluorine F due to
various etchants such as HF (aq.), NH4HF2 at room temperature [32, 33, 45, 47] Since, the hydrophilicity of

2
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 1. MXene structure.

metal present in Mn+1Xn results in the functionalization of MXene with various species such as (O, OH, F) as
depicted in equations (2), (3) and (5).
Mn + 1AX n + 3HF = AF3 + 3/ 2H2 + Mn + 1X n (1)
Mn + 1X n + 2H2 O = Mn + 1X n(OH)2 + H2 (2)
Mn + 1X n + 2HF = Mn + 1X nF2 + H2 (3)
Illustration for MXene structure is depicted in figure 1.
Mn + 1AX n + 3NH 4 HF2 = (NH 4) AlF6 + 3/ 2H2 + Mn + 1X n (4)
Mn + 1X n + a NH 4 HF2 + bH2 O = (NH3)c (NH 4)d Mn + 1X n(OH)x Fy (5)

These functional groups greatly affect the physio-chemical properties of the final resulted product (MXene).
Hence, exfoliation and etching leads to the termination of MXene with OH, O, and F groups and thus, transit the
behavior of MXene from metallic to semiconducting [45]. However, in the case of etching with HF, one more
step of delamination is necessary since the etching and exfoliation do not occur simultaneously. Since HF is a
very strong acid there is another route reported in the literature [45] of preparing MXene from in situ HF such as
LiF, NaF, and KF which are used with hydrochloric acid (HCl). This method starts by adding MAX powder in
fluoride salt along with HCl solution at room temperature for a few hours, which results in a clay-like product
after several washing cycles [45]. Further, the clay-like product can be transformed into different morphologies
by post-processing. However, the reaction of fluoride salts with HCl results in HF, shows that fluoride formation
is necessary for the production of MXene. During the reaction of HCl with the fluoride salts, intercalating the
metal cations (e.g., Li+, Na+, and K+), increases the interlayer spacing between the MXene layers. Such
intercalation cannot be possible if HF is used directly. There are several factors that can affect the etching process
are MAX structure, bonding between the atoms, and size of the particle, etc. Moreover, etchants other than HF if
used such as (e.g. LiF, HCl and NH4HF2) [48] took a long time for complete exfoliation. This is due to the fact
that the in situ intercalation of NH+ +
3 and NH4 species between MXene layers leads to the delamination of the
bundles of MXene sheets into individual multilayer sheets. Hence, in this case, no additional step for
delamination is required since exfoliation and etching occurred parallelly. Delamination and etching are the two
main factors that affect the properties of the MXene flakes [49] such as flake quality, crystallinity, defects,
thickness, and functionalization of the surface. Usually, smaller/multi-layered MXene flakes can be prepared by
delaminating with sonication and the lower concentration of LiF, whereas large mono-layered MXene flakes can
be prepared using more concentration of LiF since the use of higher concentration LiF leads to both exfoliation
and etching as shown in figure 2 [50].
Hence, multilayer MXene flakes can be separated into mono/few-layer flakes even without sonication.
Presently, the most promising methods of delamination in terms of efficiency include organic intercalating
molecules such as DMSO and isopropyl alcohol [51]. In 2011, the first multilayer MXene is synthesized by
etching A layer selectively [52]. Thereafter in 2012, new members of the MXene family appeared e.g. Ti2CTx,
(Ti, Nb)2CTx [53] and (V, Cr)3C2Tx [54]. Then, later on, delaminated single-layer MXene, small flake, double M
MXene and ordered divacancies (Mo1.3CTx) have evolved. According to the literature, for synthesizing MXenes,
Ti3C2Tx was considered as a pillar for further investigations (termed as Ti3C2Tx). To date, MXene family [34]
includes Ti3C2, Ti2C, V2C, Cr3C2, Fe2C, Nb4C3, Nb2C, Mo1.33C, Mo2C, Hf 3C2, (V2C, Cr2C, and Ta2C), Cr2N,

3
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 2. Synthesis route of MXene flakes [50].

Figure 3. Shows layered morphology of (A) Nb2CTx; (B) V2CTx [56].

Ti4N3, etc has been synthesised. If special attention will be given to the materials, variety of new MXene are
expected to be discovered in the future.

3. Application of MXene in batteries

Lithium-ion batteries (LIBs) are considered to be a promising candidate in the area of electrical vehicles.
Graphite is used mostly as anode material in the LIBs because of its excellent properties such as cost-
effectiveness, good stability, and high electronic conductivity. However, the intercalation of lithium-ion resulted
in the specific capacity of battery limited to only 372 mAh g−1 while graphite as anode [51]. Naguib et al were the
first to publish the possibility for the MXenes usage in LIBs as anode [33]. This newly discovered material shows
an increase in the surface area by approximately 10-fold as compared to graphene or MAX (Ti2AlC). Also, it
shows that there was an increase in the specific capacity to 225 mAh g−1, which was five times greater than the
MAX phase because of the greater surface area, open structure, and weak bonds between various MXene layer
elements in the Ti2C structure. Also, the Li+ ions occupy the interlayer spacing between the sheets of Ti2C. Thus,
the available [55] current state-of-the-art anode materials had a better performance than graphene which leads
to an idea of exploring new MXene based electrode materials. Afterward, niobium and vanadium carbides were
developed as an electrode material for lithium-ion batteries by Naguib et al by removing the Al layer selectively
from Nb2AlC and V2AlC compounds. The reversible capacity of 170 and 260 mAh g−1 as shown by Nb2CTx and
V2CTx at 1C, respectively [56]. As with the exfoliated graphite, similar results of layered morphology are given by
new carbides as shown in figures 3(A) and (B). In addition, high cycling rates of 10 C were also withstanding by
both electrode materials which shows that a fast Li diffusion can be carried out between the materials having
layered structure.
Afterward, computational (DFT) studies showed the possibility of Ti3C2 MXene and its derivatives such as
Ti3C2F2 and Ti3C2(OH)2 as anode materials for LIBs by Tang et al [55]. In their work, the impact of electronic
properties and intercalation on bare (Ti3C2), fluorinated (Ti3C2F2), and hydroxylated (Ti3C2(OH)2) surfaces due
to Li-ion was investigated. Further, the investigation of Li adsorption and Ti3C2 diffusion behavior was
performed. Because of the low energy barrier and small path length, it was observed that it is easy for Li-ions to

4
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 4. Synthesis of MXene from MAX and increase in the interlayer spacing by first intercalating and then (de)intercalating
Na+ion without any significant change in interlayer distance [64].

migrate on the Ti3C2 surface but for other derivatives of MXene such as Ti3C2Tx (T=F or OH), a higher
diffusion barrier was observed because of the retardation of the surface T groups. In the case of Ti3C2 derivatives,
the Li-ion smooth migration was prevented by the bulky OH groups. Hence, it was concluded that the MXene
material would be a reliable candidate for LIBs as anode due to its various properties such as high electrical
conductivity, low diffusion barrier, and large theoretical capacity (320 mAh g−1). Due to the intercalation and
delamination of the surface-functionalized Ti3C2 material by hydrazine and N, N-dimethyl formaldehyde, the c
lattice parameter was increased as shown in SEM image [49]. Also, the enhanced rate capability is shown due to
intercalation in Li-ion batteries.
Since the intercalation process is discussed for a long time to store charge in batteries because lithium can
offer a large energy density. However, to optimize electrochemical performance further, more research has to be
done for understanding the mechanism of lithiation and de-lithiation for MXene in detail. But still, it is very
difficult for transportation and storage of bigger sized cations without affecting the crystal structure. Moreover,
the application of LIBs is greatly reduced in energy storage and conversion applications due to the limited
availability of natural deposits of lithium, its safety and production cost [57, 58] and thus leads to the generation
of non-lithium-ion battery (NLB) systems such as sodium-ion, potassium-ion, Magnesium-ion, and Calcium-
ion batteries, etc [59–62]. Hence, new MX compounds were developed by Lukatskaya et al on the basis of 2D
titanium carbide layered structure which was capable of accommodating a variety of cations (e.g. Na+, K+, NH+ 4,
Mg+, +
2 and Al3 ) electrochemically from their aqueous salt solutions [63].
The main advantage of these batteries is due to their abundance, large storage capacity, wide negative redox
potentials, operational safety, and environmentally friendly nature. Moreover, MXene materials have
advantages such as high electrical conductivity, large surface area and tendency to accommodate a variety of
cations e.g. Na+ [55]. Hence, Wang et al published that in Na-ion hybrid capacitors, the Ti2CTx MXene can act as
an anode [64]. The intercalation/adsorption of Na ions into/onto the surface of MXene nanosheets enhances
the interlayer distance between the MXene layers from 7.1 to 10.1 Å as can be seen from figure 4. Afterward, it
was found by Dall Agnese et al that when V2C MXene was compared with Ti2C, their electrochemical behavior is
similar [65, 66]. Since, till now major attention was aimed at the usage of these materials as anode electrodes. But
it was presented by Dall Agnese et al that from the large family of MXenes, V2CTx can also be used as a cathode
electrode material [65]. The hybrid asymmetric supercapacitor was fabricated with anode as hard carbon and
V2CTx as a cathode. The device delivered the 50 mAh g−1 for a 3.5 voltage window. It was depicted that the
intercalation of Na-ions between the V2CTx layers had the same performance as intercalating Li-ions. Hence,
V2CTx MXene can act as a promising positive material with a large operating voltage window. A flexible and
conductive Hf3C2Tz MXene was synthesized by Zhou et al from Hf3[Al(Si)]4C compound by removing Si alloyed
Al–C sublayer selectively [67]. The volumetric capacities of 1567 and 504 mAh cm−3 had been displayed by the
as obtained 2D Hf-containing MXene material in lithium-ion and sodium-ion batteries for 200 mA g−1 current
density, showing that Hf-containing MXene material can be the best alternative. There is one more alternative
present besides lithium-ion batteries and non-lithium ion batteries is the lithium sulphur batteries (LSBs). These
batteries are considered to have a bright future in the energy storage devices because of their large theoretical
capacity (1675 mAh g−1), large availability, and greater values of specific energy density (2600 Wh kg−1) [68, 69].
However, there are some drawbacks associated with sulfur batteries such as sulfur loss, poor cycle life, and

5
 Mater. Res. Express 7 (2020) 022001
Table 1. Comparison of different materials in terms of the capacitance when used in batteries along with their advantages.

Anode Capacitance Application Advantages References

graphite 372 mAh g−1 li-ion Cost effectiveness, good stability, and high electronic conductivity [51]
Ti3C2Tx 225 mAh g−1 li-ion Surface area increased approximately by 10-fold and specific capacity by five times as compared to graphene or MAX (Ti2AlC) due to greater [33]
6

surface area, open structure, and weak bonds between various MXene layer elements
Nb2CTx 170 mAh g−1 li-ion Fast Li diffusion can be carried out between the materials having a layered structure because of the high cyclic rate of 10C. [56]
V2CTx 260 mAh g−1 li-ion Fast Li diffusion can be carried out between the materials having a layered structure because of the high cyclic rate of 10C. [56]
Hf3C2Tz 1567 mAh cm−3 li-ion The good candidate as an anode material [67]
Hf3C2Tz 504 mAh cm−3 Na-ion The good candidate as an anode material [67]
S/Ti2C 1200 mAh g−1 S-ion MXene mono/few layers bind the soluble Li2Sn species strongly, therefore, avoiding their dissociation into the electrolyte [71]
Ti3C2 320 mAh g−1 Li-ion Low energy barrier and small path length, let the easy migration of Li ions on the Ti3C2 surface but a higher diffusion barrier was observed for [55]
other derivatives of MXene such as Ti3C2Tx (T=F or OH) because of the retardation of the surface T groups.
Ti3C2Tx 40 mAh g−1 Na-ion The intercalation/adsorption of Na ions into/onto the surface of MXene nanosheets enhances the interlayer distance between the MXene [64]
layers from 7.1 to 10.1 Å
V2CTx (as a cathode) 50 mAh g−1 Na-ion Intercalation of Na-ions between the V2CTx layers had the same performance as intercalating Li-ions. [65]

R Garg et al
Mater. Res. Express 7 (2020) 022001 R Garg et al

dissolution of electrolytes. All these drawbacks prove to be the major hurdles in sulfur-based batteries, hence
limits their performance. In order to tackle these problems, efficient electrode material for hosting sulfur has to
be discovered. The study of titanium carbide-based MXene (Ti2CO2) had been done by Zhao et al as the host
material of Li2Sn species for Li–S batteries by carrying the DFT computations. It had been concluded that
MXene mono/few layers bind the soluble Li2Sn species strongly, therefore, avoiding their dissociation into the
electrolyte [70]. Similarly, the performance of LSBs was significantly improved by Ti-based MXene (Ti2C) as
discovered by Rao et al using DFT calculations [71]. Due to the interaction of lithium sulfides (Li2Sm) on the
surface of functionalized MXene, their bond between Titanium and Sulphur becomes stronger that helps in
preventing sulfur dissolution. Later on, it was reported that because of the strong bond between Ti-based
carbides functionalized groups and the polysulfide species due to the high metallic conductivity, MXene appears
as a promising candidate as hosts for the sulfur battery [71]. The S/Ti2C composites with 70 wt% showed cycling
performance of long-term stability and retaining capacity up to 80% after 400 cycles at 2C with a specific
capacity of around 1200 mAh g−1 current density at 5C. Table 1 summarized the capacitance and advantages of
different materials used for anode and cathode electrodes for different batteries applications which have been
discussed in this section.

4. Effect of interlayer distance between MXene layers in supercapacitors

2D layered electrode materials have the ability to accommodate different sized cations. This ability to
accommodate the cations is known as intercalation. A variety of MXene is synthesized in the literature having
structural similarities to graphene. A large number of intercalants such as DMSO, urea, hydrazine has been used
for the intercalation. The most common intercalant used was hydrazine monohydrate N2H4 H2O (HM)
dissolved in N, N-dimethylformamide (DMF) that has increased the interlayer spacing from 7.2 to 10.3–10.4 Å
[72, 73] To intercalate HM in fluorine terminated MXene, MXene powder is mixed in HM or HM and DMF and
stirred for one day. After the treatment of MXene with the HM, the suspension is filtered, for intercalation, the
washing of the sediment is done with DMF instead of ethanol [33].
Intercalation using DMSO and urea follows the same procedure [49]. MXene powder is first mixed with
DMSO or urea and then the sediment is collected and dried in vacuum. For delamination, DMSO is used. After
the stirring of f-Ti3C2 with DMSO at R.T, the colloidal suspension was centrifuged to separate the intercalated
powder from the liquid DMSO. After decantation of the supernatant, deionized water was added to the residue.
After bath sonication of the suspension, centrifuging was carried out and the supernatant was filtered using a
porous membrane filter and dried in the oven at 70°C overnight, resulting in d-MXene ‘paper’ that detach easily
from the membrane.
Using angle spinning NMP technology and DFT calculations, Satoshi Kajiyama et al illustrated the
intercalation of Na-ion in Ti3C2Tx nanosheets [74]. It had been shown that the reversible intercalation and
deintercalation of Na ions were exhibited by MXene nanosheets in non-aqueous Na based electrolytes. It was
also demonstrated that after the first sodiation, there was an increase in the interlayer spacing and then after
sodiation, there was intercalation and deintercalation of desolvated sodium ions. However, the pillared effect of
Na ions and the swollen effect caused by the penetration of solvent molecules between the MXene sheets during
the complete sodiation and desodiation process, the interlayer distance was maintained. Since during the
intercalation and deintercalation reactions of sodium ions, no structural change is observed since Ti3C2Tx
exhibits excellent rate capability and capacitive retention over 100 cycles. After the treatment of Ti3C2Tx with
hydrofluoric acid for 15 h at room temperature, there was a shift in the (002) peak from higher to a lower angle
which showed an increase in the c-lattice parameter from 9.25 to 9.67 Å as depicted in figure 5. Then during the
first sodiation process, the (002) peak further shifts to a lower angle, implying a relative expansion in the
interlayer spacing from 9.7 Å (pristine) to 12.5 Å.
A publication illustrating the effect of metal ion intercalation on the vibrational dynamics of water molecules
was presented by Naresh C. Osti et al [75] Since the partial removal of water molecules and bonding between
surface-functionalized groups and remaining water molecules leads to a reduction in the mobility of water
molecules. In bare MXene, the 002 peak was found to be at 19.88 Å. After intercalation, there was a shift in the
002 peak to a lower angle, presenting an increase in the interlayer spacing. As compared to the change in the
spacing between bare MXene layers, the intercalation of metal ions shows different results. After vacuum
annealing, it is observed that Intercalating MXene layers with potassium ions lead to a very small decrease in the
c-lattice parameter whereas intercalation with sodium ions show two peaks from which one was narrow and one
was broad with 002 peak at 23.98 Å and 21.22 Å, respectively as compared to the results without annealing. Also,
the results obtained with lithium intercalated MXene show the 002-peak change from 24.63 Å to 19.88 Å as
illustrated in figure 6.

7
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 5. XRD images for corresponding MAX and Ti3C2Tx [74].

Figure 6. XRD pattern of bare MXene and before and after metal ions (Li+, Na+ and K+) intercalated MXene after vacuum annealing
at 110oC with their respective s-lattice parameters [75].

Effect of cation intercalation in controlling the actuation properties of MXene paper electrodes was
published by Jeremy Come et al [76]. It was observed that intercalation of lithium, sodium, and magnesium lead
to electrode contraction whereas there a small increase in the interlayer spacing was observed upon potassium
intercalation. Following are the results obtained for the change of height with a charge to ionic radius ratios such
as 1.67 Å for lithium, 1.05Å for sodium, 0.75Å for potassium and 2.78Å for magnesium [77]. Since lithium,
sodium, and potassium are monovalent ions, there was a decrease in the amplitude at a large ionic radius. The
effective radius of these hydrated ions is 3.82 Å for lithium, 3.58Å for sodium, 3.31 Å for potassium and 4.28Å for
magnesium respectively [78]. It was observed that during intercalation, the hydration shell around the ion was
completely or partially removed. As for dry MXene paper, as shown in figure 7(A), the d spacing of 10.04 Å is
present corresponding to the (0002) peak at 8.83˚. In figure 7(B) it was shown that during Li+ intercalation, there
was a shifting of (0002) peak from higher to lower angles and during the deintercalation, the (0002) peak again
shifts from lower to higher angle showing the contraction. Thus, it was also depicted in figure 7(C) that there is a
shrinkage of the MXene layers which leads to a decrease in the interlayer spacing from 12.84 Å to 12.56 Å on Li+
intercalation, which approximately equals to 2.1%. Since the decrease in the d-spacing is lower than the
macroscopic contraction recorded previously, additional electrostatic forces must play a role in the interactions
between MXene sheets.
It was demonstrated by Meng-Qiang Zhao et al regarding the storage of magnesium ions in MXenes. The as-
fabricated 3D microporous flexible and conductive MXene films were tested as a cathode in magnesium ion
battery after the intercalation of magnesium ions from a magnesium-based electrolyte [79, 80]. A fabricated
composite Mg0.21Ti3C2Tx electrode shows capacitance values of 210 mAh g−1, 140 mAh g−1 and 55 mAh g−1
respectively at capacities of 0.5 C, 1 C, and 5 C. It was shown that after intercalating Mg2+ ion between the

8
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 7. (A) XRD patterns of the dry MXene paper; (B) 1 M Li2SO4; (C) Lithium sulphate spacing versus potential [76].

Figure 8. XRD patterns showing the comparison between before and after the intercalation of Mg2+ ions [80].

MXene layers the (002) peak shifts from 6.5° to 5.7°. Hence, it shows that the intercalation of Mg2+ increases the
interlayer spacing from 13.6 to 15.5 Å as shown in figure 8. A method is developed by Li et al for intercalating
cations and modifying the surface for enhancing the capacitance of Ti3C2Tx MXenes, which was then resulted in
the 200% improvement in the capacitance [81]. After the etching of aluminum layer from the Ti3AlC2 precursor,
the final MXene (Ti3C2Tx) material is terminated by OH and F functional groups, then treated with bases having
varied cationic radii such as KOH. Due to this, the bond becomes unstable between titanium and fluorine. F
terminal groups are then replaced by hydroxyl groups due to the intercalation of K+ ions between the MXene
layers. Hence, due to the removal of functionalized groups such as F for MXene treated with KOH, the
electrochemical performance is improved. Due to the large interlayer distance and lower fluorine concentration
at the KOH-treated Ti3C2 MXene surface, the capacitance value obtained is 517 F g−1 at a current density of
1 A g−1 because of the K+ ions intercalation. Hence, the effective route to enhance the capacitance is by
combining both the mechanisms of cation intercalation and surface group modification. Because of the cation
intercalation and the interlayer spacing improvement, further efforts were emphasized on bringing larger
cations that can drastically modify the internal structure of the host [74, 82, 83]. There is a large possibility in the
intercalation of polyatomic cations such as alkylammonium (AA) is by Ghidiu et al into MXene materials [45].
Thus, better electrolyte access can be introduced by intercalating large-sized cations into the interlayer spacing of
charge storage devices. The effect of interlayer spacing for different materials on the supercapacitor device
performance is summarized in table 2. Hence, by understanding the structural effects of the intercalation,
experimental as well as theoretical measurements were performed to understand the best conditions for
intercalating large cation. Since larger cations presence reduces the specific capacitance because a dead volume
can be created in the electrode. Therefore, for some applications, larger interlayer spacing is not useful because
the larger interlayer spacing between the MXene layers is not better energy storage and conversion applications.

5. Different strategies to prepare MXene films

An additive and binder-free MXene paper electrodes were prepared by filtrating delaminated MXene sheets with
a thickness of 20–50nm as proposed by Mashtalir et al [49] as illustrated in figure 9. The result shows that
340 F cm−3 capacitance was obtained with the KOH electrolyte solution [49]. It was observed that the results

9
 Mater. Res. Express 7 (2020) 022001
Table 2. Effect of interlayer distances on the electrochemical performance of supercapacitors.

Interlayer spacing Material Capacitance No. of cycles References

10

2.708 nm CTAB−Sn(IV)@Ti3C2//AC 51 F g−1 capacity retention of 71.1% after 4000 cycles at 2 A g−1 [84]
2.23 nm CTAB@Ti3C2 248 mAh g−1 100 cycles [84]
0.7 nm benzoate‐α‐Co(OH)2 70 F g−1 at 15A g−1 72% of capacitance is retained after 2000 cycles [85]
1.6 nm Dodecyl sulfate (DS)‐α‐Co(OH)2 300 F g−1 at 15A g−1 95% of capacitance is retained after 2000 cycles [85]
0.09 nm NO−3 ‐α‐Co(OH)2 33F g−1 at 15A g−1 81% of capacitance is retained after 2000 cycles [85]
8.1065 Å NiCo2O4–RGO 908 F g−1 4000 cycles [86]
2.578 nm Clay like Ti3C2Tx 900 F cm−3 10,000 cycles [87]
10 Å PPy/Ti3C2Tx 416 F g−1 at 5 mV s−1 The capacitance retention was 92% after 25,000 cycles [88]

R Garg et al
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 9. Schematic showing the fabrication of Binder and additive-free Ti3C2Tx paper electrode.

Figure 10. Schematic illustrating the adjustable properties of MXene-based functional films [89].

obtained were better than those proposed by Naguib et al for Ti2C [66] due to various properties such as large
surface area (98 m2 g−1), hydrophilic nature, and good conductivity. Also, the flexibility of the fabricated MXene
paper may open new avenues in wearable and flexible energy storage applications. It shows that these binder-free
MXene papers exhibit a specific capacity of 410 mAh g−1 at a cyclic rate of 1C and 110 mAh g−1 at a cycling rate
of 36C. Although, due to the surface functionalities such as OH and F present on the MXene sample surfaces, the
theoretical results were less as compared to measured results [55]. Since to increase the value of capacitance, the
key parameter is to have a greater surface area, but for multilayer MXene, the surface area is very low which is
approximately 23 m2 g−1 [52]. Hence for large capacitance results, it is very beneficial to delaminate the layers
for increasing the surface area. Since the formation of mono or few-layer MXene sheets of few nm thicknesses
has motivated researchers to find new avenues to fabricate various flexible energy storage devices [49, 56, 63, 66].
As reported by Ling et al flexible and highly conductive nanocomposite film was synthesized by fabricating
hybrids of MXene with polymer, as shown in figure 10 [89]. Moreover, the hybrid film possesses a large number
of advantages such as flexibility, strength, and high electrical conductivity. Among various polymers,
polydiallyldimethylammonium chloride (PDDA) was used mostly for intercalating between the MXene layers
because of its cationic nature, and polyvinyl alcohol (PVA), hydrophilic nature and presence of OH group in its
backbone. When bare MXene and hybrid of MXene with PVA and PDDA were used as electrode materials in a
supercapacitor, the results obtained for the capacitance were 300,528,296 F cm−3 respectively with 2 mV s−1
scan rate in an electrolyte solution of KOH. There was no change observed in the value of capacitance on adding
the PDDA polymer because of the poor density of the composite film relative to bare MXene. However, there
was an increase in the value of capacitance on mixing PVA polymer with MXene film. The reason for the
enhancement in the performance of PVA as compared to PDDA is because of the improved ionic transport as
well as access to MXene, along with the prevention by the PVA polymer in the restacking of MXene flakes.
Although the electrical conductivity of the composite films and the bare Ti3C2Tx is almost identical, there
were also other factors that determine the electrochemical performances of the composite film such as
restacking prevention, ionic access and their transport, degree of cationic interaction, and composite film
flexibility. Afterward, the clay-like MXene (Ti3C2Tx) was synthesized by Ghidiu et al using LiF and HCl solution
[45]. The as-synthesized MXene was rolled into thin nanosheets as shown in figure 11. When acidic electrolyte
was used, additive-free Ti3C2Tx films resulted in a volumetric capacitance of 900 F cm−3 (or 245 F g−1) [33].

11
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 11. Schematic illustrating the synthesis and applications of MXene clay.

Figure 12. (a) Device schematic of supercapacitor having spray-coated large sized(L) Ti3C2Tx at the bottom served as the current
collector followed by coating of an electroactive small sized (S) MXene film and formation of laser cut interdigital electrodes [90].

Afterward, all MXene interdigital microsupercapacitor using spray coating method is presented by You-Yu
Peng et al The large sized MXene flakes were stacked at the bottom layer used as current collectors. The small
sized MXene flakes served the top layer with various number of defects as can be seen from figure 12. As
compared to the platinum current collectors, Ti3C2Tx micro-supercapacitors showed much lower contact
resistance, larger capacitances and good rate-capabilities. The values for areal and volumetric capacitances are
∼27 mF cm−2 and 357 F cm−3, respectively, at a scan rate of 20 mV s−1. The as fabricated devices also showed
good cyclic stability and capacitance retention of 100% after 10,000 cycles [90].
A novel chemical etching strategy was developed at room temperature by Ren et al to produce porous
Ti3C2Tx [51]. The process first includes the usage of the transition metal salt (CuSO4, CoSO4, or FeSO4) for the
catalytic oxidation of MXene flakes and then the removal of the metal oxide (TiO2), which results from the
oxidation process in the oxygen-rich environment as shown in figure 13(A). It was observed that the formation
of porous MXene leads to an increase in the pore volume by 10-fold containing various pores with different sizes
in nm, and the specific surface area from 19.6 to 93.6 m2 g−1 as presented in figures 13(B) and (C). The results
obtained showed that at 0.1C, a 1250 mAh g−1 high capacity was obtained. Furthermore, during the removal of
metal oxide, there was no serious effect observed on the surface terminated (F, O, and OH) groups by using acid
etchants, suggesting that the process can be used for preparing porous structures from other MXenes. Since it
was identified that the MXenes are the promising electrode material for energy storage applications, hence more
effort has been aimed to improve their performance further by modifying their surface and by increasing active
sites and the spacing between MXene layers. Thus, when particular functional groups are removed there is a
large improvement in the electrochemical performance of MXene and an increase in the interlayer spacing.
Hence, it is observed from the previous studies that the surface termination groups have a strong impact on the
storage ability of MXenes e.g. the electrolyte ions transportation is hampered by fluorine and hydroxyl
functional groups, thus reducing the capacity of the energy storage [91].

12
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 13. (A) Mechanism of synthesising porous MXene from oxidation process in presence of oxygen rich environment; (B) and (C)
Synthesis of porous structure before and after etching through TEM images [51].

Figure 14. Bare MXene, Ti3C2Tx/PDDA and Ti3C2Tx/PVA-KOH Capacitance performance is illustrated (A) at different scan rates;
(B) 2 mV s−1 scan rate [89].

6. MXene based supercapacitors

First, Chang E. Ren et al [92] studied bare MXene and its composite films using a vacuum-assisted filtration
(VAF) method. 2.2×104 S m−1 and 2×103 S m−1 conductivity were obtained for composite Ti3C2Tx/PVA
and Ti3C2Tx/PDDA film and 2.4×105 S m−1 for bare Ti3C2Tx films. It was also observed that the capacitive
results of MXene were over 300 F cm−3 which was higher as compared to the graphene (60 ∼ 100 F cm−3) [52],
carbide-derived carbons (180 F cm−3) [63] or graphene gel films (∼260 F/cm3) [93] previously reported. Also,
the impressive volumetric capacitance was given by PVA/MXene composite with their respective values in KOH
electrolyte obtained are 528 F cm−3 and 306 F cm−3 at 2 mV s−1 and 100 mV s−1 as shown in figures 14(A)
and (B).
Leiqiang Qin et al reported Solution Processable Mo1.33C MXene and PEDOT: PSS and obtained a
maximum capacitance of 568 F cm−3, 33.2 mWh cm−3 energy density and 19470 mW cm−3 power density [94].
It was observed that the capacitance and rate capability of composite Mo1.33C MXene/PEDOT: PSS film were
enhanced as compared to both pristine Mo1.33C MXene and the nontreated Mo1.33C/PEDOT: PSS hybrids since
the treatment of the composite film with H2SO4 increases the interlayer distance. The method for obtaining
hybrid films and their fabrication in the supercapacitor is depicted in figure 15. The composite electrode treated
with H2SO4 having a 10:1 mass ratio for 24 h possesses a volumetric capacitance to a maximum of 1310 F cm−3
and 452 F g−1 at 2 mV s−1 [95]. Before this research, only a few reports were evaluated about MXene and
polymer composites as an electrode material for supercapacitor applications [88]. Later on, Sixing Xu et al [96]
reported micro supercapacitor (MSC) relies on 2D Transition Metal Carbides (MXene) thick interdigital
electrodes using MEMS technology. The larger mass loading was provided by building 300 μm thick titanium
carbide as interdigital fingers and polymer electrolyte (PE) as the electrodes. The results show that a specific
capacitance of 276 mF cm−2 and capacitance retention of 95% after 1000 cycles was observed. In order to
stabilize the structure, PE was used instead of PTFE and PVDF since the electrode surface accessibility can be
increased in PE by ions [55]. However, the increased accessibility leads to an increase in surface area and a
decrease in the ionic resistance. The interspaces between layers were filled by the polymer electrolyte.

13
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 15. Schematic illustrating the preparation of composite films and its fabrication as an electrode material in solid-state
supercapacitor [94].

Figure 16. (A) Cr/Au layer deposited as current collector; (B) SU-8 deposited as separator; (C) electrode material injected into the
trenches; (D) PVA-H3PO4 electrolyte coating.

The width of electrode fingers and the separator was 300 μm and 60 μm with electrode thickness 300 μm
respectively as shown in figures 16(A) and (B). The isolation between the electrode fingers was shown by SU-8
walls figure 16(C). The whole device cross-section as shown in figure 16(D). It was also observed that all the
spaces of the trench were filled by composite material and due to the sinking of material, a small concave is
observed in the middle during the solidification process.
Afterward, the whiskers of the nanocrystalline ε-MnO2 were prepared by Raghavan Baby Rakhi et al [97] on
nanosheet surfaces (ε-MnO2/Ti2CTx and ε-MnO2/Ti3C2Tx) of MXene by using direct chemical synthesis to
make aqueous pseudocapacitors using nanocomposite electrodes (figure 17). Since the specific capacitance of
the composite electrode was increased from 32.4 to 210.9 F g−1 due to the ε-MnO2 nanowhiskers at a scan rate of
10 mV s−1 as shown in figures 18(A) and (B). Also, at the end of 10,000 cycles, the as-fabricated composite
supercapacitor maintained maximum capacitance till 87.7% whereas pure MnO2 whiskers maintain only 74.5%
[52] of maximum capacitance.
Greater volumetric energy density by annealing MXene nickel oxide asymmetric supercapacitor was
obtained by Qi Xun Xia et al using the hydrothermal method [98]. It exhibits 92.0 mAh cm−3 and
53.9 mAh cm−3 specific capacitance at current densities of 1 A g−1 and 10 A g−1 respectively with an energy

14
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 17. Preparation mechanism of MnO2/MXene composite [97].

Figure 18. (A) Specific capacitances of bare MXene and ε-MnO2 nanowhiskers/MXene at different current densities; (B) CV profile of
ε-MnO2/Ti3C2Tx_Ar composite samples at different scan rate [97].

Figure 19. (a) as-fabricated Ti3C2Tx MXene after DMSO treatment; (b) the as-fabricated Ni-dMXNC [98].

density of 1.04×10−2 W h/cm3 for the power density of 0.22 W cm−3, and 72.1% cycling stability with
retention after 5000 cycles. As compared to the bare MXene, the as-fabricated TiO2/C-Ti3C2Tx MXene display
lower resistivity and a bigger specific surface area, which was an important parameter in enhancing the
supercapacitor performance. DMSO treatment causes the exfoliation of Ti3C2Tx MXene obtained as depicted in
figure 19(a), which shows more number of slots than before. Since the single-layered MXene has only 1nm
thickness, the MXene flakes produced by using DMSO treatment results in 10–70 nm thick, hence DMSO
results in many or few 10–70 layers of multilayer MXene. The FESEM image of an as-fabricated device is
demonstrated in figure 19(b) which shows that there is an enhancement in the dimensions (horizontally as well

15
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 20. (A) current voltage profiles at 1 mV s−1 scan rate; (B) specific capacitances versus scan rate of Ti3C2Tx and N-Ti3C2Tx in
1M H2SO4; (C) capacitance versus potential graph at a scan rate of 1 mV s−1; (D) specific capacitances versus scan Ti3C2Tx and
N-Ti3C2Tx in 1 M MgSO4 electrolyte [100].

as vertically) of the single-layered sheet because of the successful addition of the NiO nanosheets. The resistance
measurements between bare MXene and Ni-dMXNC indicates the better conductivity, enhanced surface area,
the active NiO covering, increase in the electrode/electrolyte interfacial contact area and short diffusion path of
Ni-dMXNC as compared to pure Ti3C2Tx MXene.
Qiuyan Yang et al [99] reported an MXene-based continuous fibers using wet-spinning assembly strategy
through a synergic effect between MXene sheets and graphene oxides liquid crystals. There was an orderly
alignment of MXene sheets between the crystalline template of liquid graphene oxides and them assembled into
hybrid fibers. It was shown that there was an increased in the electrical conductivity (2.9×104 S m−1) and
volumetric capacitance (586.4 F cm−3) of the as-constructed integrated fiber supercapacitor as compared to
neatly reduced graphene fibers (16.4 F cm−3). Later on, as a promising electrode material, it was synthesized for
the first time by Yangyang Wen et al [100] by doping nitrogen in two-dimensional MXene (N-Ti3C2Tx) by post-
etch annealing Mxene in the presence of ammonia. At 200 °C, it was demonstrated that there was a remarkable
increase in the c-lattice parameter by encapsulating nitrogen in the MXene structure as a heteroatom from
1.92 nm in bare Mxene to 2.46 nm in N-doped MXene. Moreover, it was depicted that under ambient
conditions, the MXene with doped nitrogen shows a sudden improvement in the electrochemical capacitances
from 192 F g−1 and 82 F g−1 in 1 M H2SO4 and 1 M MgSO4 respectively, which was more than those compared
to bare MXene showing electrochemical capacitance of 34 F g−1 and 52 F/g in 1 M H2SO4 and 1 M MgSO4.
Furthermore, it was shown in figure 20(A) that the results of cyclic voltammetry (CV) in 1 M H2SO4 was not
ideal as compared to 1 M MgSO4 electrolyte. Instead, the CV profiles in H2SO4 electrolyte show peaks at −0.2 V
to −0.1 V potential. It can be described that these peaks may be due to the bonding/debonding of H+ions with
the terminal oxygen in the Ti3C2Tx electrode which further introduced the pseudocapacitance due to the change
in valance state of the Ti element. Different results of gravimetric capacitance were obtained for the nitrogen-
doped MXene in 1M H2SO4 electrolyte at different temperature e.g. 34 F g−1 for bare Ti3C2Tx, 192 F g−1 for N-
Ti3C2Tx at 200°C, 45 F g−1 for N- Ti3C2Tx at 300°C, 20 F g−1 for N- Ti3C2Tx at 500 °C and 10 F g−1 for N-
Ti3C2Tx at 700 °C as shown in figure 20(B). It is observed that the results of specific capacitance for some of the
MXene based electrodes were less as compared with bare MXene electrodes due to the small fraction of TiC
phase impurity present in the Ti3C2Tx for different synthesis conditions. However, these results demonstrate a
remarkable improvement of 460% in the specific capacitance at 200 °C and 300 °C because of the N-doping by
ammonia treatment than at 500 °C and 700 °C because of the pseudocapacitive contributions by the
N-containing functionalized groups and interlayer distance improvement. At varied scan rates from 1 mV s−1 to
50 mV s−1, it was observed that rectangular-shaped CV is obtained in 1M MgSO4 (figure 20(C)). It was shown
that the maximum gravimetric capacitance reaches 52 F g−1 at 1 mV s−1 for the MXene electrodes, which was
then decreased to a lower value at higher scan rates as shown in figure 20(D). As compared to the H2SO4
(0.26 S cm−1) [101], the conductivity of MgSO4 (0.051 S cm−1) [63] is less and so is the capacitance. Na Zhang
et al decorated 2D Titanium Carbide with Ag-Nanoparticles [102]. The composite device possesses a specific
surface area of 107 m2 g−1, 332.2 mF cm−2 areal capacitance at a scan rate of 2 mV s−1, 63.2% of the capacitance
retention till 100 mV s−1, cycling stability with 87% of capacitance retention at more than 10,000 cycles. The

16
Mater. Res. Express 7 (2020) 022001 R Garg et al

Figure 21. (A) Steps illustrating the preparation of Ti3C2Tx/Ag NP hybrid film electrodes; (B) images depicting the clear tyndall effect
of Ag NPs, Ti3C2Tx NSs, and the mixture dispersions with laser light; (C) Wrapping of Ti3C2Tx/Ag NP hybrid film on glass tube
showing its flexible nature [102].

Table 3. Comparison of electrochemical performance of different 2D materials.

Materials Capacitance Cycles References

Ti3C2Tx 900 F cm−3 at 2 mV s−1 10,000 cycles [45]

FeS2 4200 mA h g−1 at 4 A g−1 20,000 cycles [103]
Ti2CTx 175 mAh g−1 at 20 mA g−1 50–100 cycles [64]
RGO film 143 mAh g−1 at 0.05 A g−1 50,000 cycles [104]
MoS2 nanosheets 235 F g−1 at 5 mV s−1 5000 charge/discharge cycles at 1 A g−1 [105]
VN/CNT 715 mF cm-2 at 1 mA cm−2 5000 cycles at 90˚ bent. [106]

composite device also delivers energy density to a maximum of 121.4 μWh cm−2 and a power density of
17395 μW cm−2.
The preparation of Ag NPs/MXene was shown in figure 21(A). The digital photographs of Ag nanoparticles,
MXene nanosheets, and their mixture dispersion were shown in figure 21(B) respectively. During colloidal
dispersion, a sidelight beam was incident and a strong Tyndall scattering effect was observed. In general, due to
the strong bonding between the Ag nanoparticles, there was a difficulty in their dispersion. Additionally, due to
its flexible nature, it can be easily wrapped over the glass tube without any change in its structure, as depicted in
figure 21(C). As it acts only as a conductive spacer in hybrid with the MXene, it does not show any contribution
in capacitance. Hence, when a large amount of Ag nanoparticles is mixed, it reduces the flexibility of the hybrid
paper. Table 3 shows the comparison of electrochemical performance of different 2D materials which have been
used in supercapacitor.

7. Conclusion and future scope

The high demands of electrochemical energy storage devices are acquired by devoting attention to the
development of advanced electrode materials. In the past few decades, drawbacks of various electrode materials
such as carbon and its derivatives, metal oxides and conducting polymers discovered the interest in the
exploration of new electrode materials. Since the benefits of individual layers in 2D materials have led to the
discovery of new 2D materials. From this aspect, a new 2D electrode material MXene is investigated in 2011.
Moreover, MXene shows excellent electrochemical properties such as brittleness, high melting point, oxidation
resistant, strong electrical and thermal conductivity, hydrophilic nature, compositional variability, large surface
area, and tendency to host a large variety of intercalants. Hence, it has been developed as an alternative to the
previous electrode materials. In this review paper, recent technologies towards the synthesis of 2D MXene and
their utilization as electrode material in energy storage devices have been illustrated. In general, the process of
preparing MXene involves selective etchings Al layer from the MAX phase using HF, followed by separating the
multilayer MXene into a few layers by sonication. Besides HF, other etchant mixtures that are less toxic such as
LiF and HCl than HF are used to successfully etch A layer from MAX phase. Multilayered MXenes with
hydrophilic surface thus can be yielded into different morphologies with different functional groups e.g.
hydroxyl, oxygen, and fluorine. However, new approaches are needed to be investigated for the preparation of

17
Mater. Res. Express 7 (2020) 022001 R Garg et al

fluoride-free MXenes. Since, the advantage of large interlayer spacing between MXene layers, different sized
cations are intercalated into the MXene surface proving MXene as the best candidate for the energy storage
device as an electrode material. Using MXene in the LIB batteries have led to high capacity and stability. In spite
of using lithium, there are a variety of cations available e.g. sodium, potassium, magnesium, etc that are
intercalated between the MXene layers showing them as the best candidate for hybrid devices. Furthermore, the
intercalation of larger sized cations has not fully explored because there can be a tendency that large interlayer
cations lead to low conductivity. Thus, affecting the charge transfer and easy diffusion of the electrolyte ions.
Also, the other composites of MXenes with the conducting polymers are yet needed to be explored. These hybrid
characterizations thus contribute towards the applications of MXene in the future. Furthermore, the conductive
interlayer spacers added to the MXene layers can also provide an additional route for electron-conduction by
keeping suitable interlayer separations. Hence, contributing to the improvement of electrochemical
performance. Hence, MXene, a new 2D material shows a great future as electrode material in energy storage
devices. Because of several advantages such as avoiding the problem of restacking, enhanced electronic
conductivity and stability, and easy ion/electron transfer, these MXene-based hybrids open new research in the
class of energy storage and conversion applications. Hence it is reviewed that the recent advancement in the
synthesis, effect of interlayer distance in energy storage devices and MXene hybrid would lead to a useful path for
further investigations towards energy storage applications.

ORCID iDs

Mohit Agarwal https://orcid.org/0000-0002-3934-560X

References
[1] Chu S and Majumdar A 2012 Opportunities and challenges for a sustainable energy future Nature 488 294
[2] Dunn B, Kamath H and Tarascon J-M 2011 Electrical energy storage for the grid: a battery of choices (supporting online material)
Science (80-.) 334 928–35
[3] Westerlund S 1994 Capacitor theory IEEE Trans. Dielectr. Electr. Insul. 1 1–3
[4] Pandolfo A G and Hollenkamp A F 2006 Carbon properties and their role in supercapacitors J. Power Sources 157 11–27
[5] Danilovic N et al 2014 Using surface segregation to design stable Ru-Ir oxides for the oxygen evolution reaction in acidic
environments Angew. Chemie Int. Ed. 53 14016–21
[6] Oh A, Sa Y J, Hwang H, Baik H, Kim J, Kim B, Joo S H and Lee K 2016 Rational design of Pt–Ni–Co ternary alloy nanoframe crystals as
highly efficient catalysts toward the alkaline hydrogen evolution reaction Nanoscale 8 16379–86
[7] Yoon J, Park J, Sa Y J, Yang Y, Baik H, Joo S H and Lee K 2016 Synthesis of bare Pt 3 Ni nanorods from PtNi@ Ni core–shell nanorods
by acid etching: one-step surfactant removal and phase conversion for optimal electrochemical performance toward oxygen
reduction reaction Cryst. Eng. Comm. 18 6002–7
[8] Yang L, Vukmirovic M B, Su D, Sasaki K, Herron J A, Mavrikakis M, Liao S and Adzic R R 2013 Tuning the catalytic activity of Ru@Pt
core–shell nanoparticles for the oxygen reduction reaction by varying the shell thickness J. Phys. Chem. C 117 1748–53
[9] Jin H, Lee K W, Khi N T, An H, Park J, Baik H, Kim J, Yang H and Lee K 2015 Rational synthesis of heterostructured M/Pt (M=Ru
or Rh) octahedral nanoboxes and octapods and their structure-dependent electrochemical activity toward the oxygen evolution
reaction Small 11 4462–8
[10] Debe M K 2012 Electrocatalyst approaches and challenges for automotive fuel cells Nature 486 43
[11] Gasteiger H A, Kocha S S, Sompalli B and Wagner F T 2005 Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen
reduction catalysts for PEMFCs Appl. Catal. B Environ. 56 9–35
[12] Yan Y, Xia B Y, Zhao B and Wang X 2016 A review on noble-metal-free bifunctional heterogeneous catalysts for overall
electrochemical water splitting J. Mater. Chem. A 4 17587–603
[13] Burke M S, Enman L J, Batchellor A S, Zou S and Boettcher S W 2015 Oxygen evolution reaction electrocatalysis on transition metal
oxides and (Oxy)hydroxides: activity trends and design principles Chem. Mater. 27 7549–58
[14] Hunter B M, Gray H B and Müller A M 2016 Earth-abundant heterogeneous water oxidation catalysts Chem. Rev. 116 14120–36
[15] Wang J, Xu F, Jin H, Chen Y and Wang Y 2017 Non-noble metal-based carbon composites in hydrogen evolution reaction:
fundamentals to applications Adv. Mater. 29 1605838
[16] Reddy A L M, Gowda S R, Shaijumon M M and Ajayan P M 2012 Hybrid nanostructures for energy storage applications Adv. Mater.
24 5045–64
[17] Gamby J, Taberna P L, Simon P, Fauvarque J F and Chesneau M 2001 Studies and characterisations of various activated carbons used
for carbon/carbon supercapacitors J. Power Sources 101 109–16
[18] An K H, Kim W S, Park Y S, Choi Y C, Lee S M, Chung D C, Bae D J, Lim S C and Lee Y H 2001 Supercapacitors using single-walled
carbon nanotube electrodes Adv. Mater. 13 497–500
[19] Zhang L Reviews X Z-C S and 2009 U 2009 Carbon-based materials as supercapacitor electrodes pubs.rsc.org 38 2520–31
[20] Liu C, Yu Z, Neff D, Zhamu A and Jang B Z 2010 Graphene-based supercapacitor with an ultrahigh energy density Nano Lett. 10
4863–8
[21] Xia H, Meng Y, Yuan G and Cui C 2012 A symmetric RuO2/RuO2 supercapacitor operating at 1.6 V by using a neutral aqueous
electrolyte Electrochemical and Solid-State Letters 15 60–3
[22] Demarconnay L, Raymundo-Piñero E and Béguin F 2011 Adjustment of Electrodes Potential Window in an Asymmetric Carbon/
MnO2 Supercapacitor Journal of Power Sources 196 580–6
[23] Conway B E 1991 Transition from ‘supercapacitor’ to ‘battery’ behavior in electrochemical energy storage J. Electrochem. Soc. 138
1539–48
[24] Laine J and Yunes S 1992 Effect of preperation method on the pore size distribution of AC from coconut shell Carbon N. Y 30 601–4

18
Mater. Res. Express 7 (2020) 022001 R Garg et al

[25] Yang F, Xu M, Bao S-J, Wei H and Chai H 2014 Self-assembled hierarchical graphene/polyaniline hybrid aerogels for electrochemical
capacitive energy storage Electrochim. Acta 137 381–7
[26] Yu G, Hu L, Liu N, Wang H, Vosgueritchian M, Yang Y, Cui Y and Bao Z 2011 Enhancing the supercapacitor performance of
graphene/MnO2 nanostructured electrodes by conductive wrapping Nano Lett. 11 4438–42
[27] Mas-Balleste R, Gomez-Navarro C, Gomez-Herrero J and Zamora F 2011 2D materials: to graphene and beyond Nanoscale 3 20–30
[28] Sheberla D, Bachman J and Elias J Materials C S-N and 2017 U 2017 Conductive MOF electrodes for stable supercapacitors with high
areal capacitance Nature. Com 16 220
[29] Behera J N, Tripathy R K and Samantara A K 2019 Cobalt metal organic framework (Co-MOF): a bi-functional electro active material
for oxygen evolution and reduction reaction Dalt. Trans. 48 10557–64
[30] Ruiz V R, Suárez-Guevara J and Gómez-Romero P 2012 Hybrid Electrodes Based on Polyoxometalate-Carbon Materials for
Electrochemical Supercapacitors 24 35–8
[31] Hao C et al 2016 Flexible all-solid-state supercapacitors based on liquid-exfoliated black-phosphorus nanoflakes Adv. Mater. 28
3194–201
[32] Naguib M, Mashtalir O, Carle J, Presser V, Lu J, Hultman L, Gogotsi Y and Barsoum M W 2012 Two-dimensional transition metal
carbides ACS Nano 6 1322–31
[33] Naguib M, Kurtoglu M, Presser V, Lu J, Niu J, Heon M, Hultman L, Gogotsi Y and Barsoum M W 2011 Two-dimensional
nanocrystals produced by exfoliation of Ti3AlC2 Adv. Mater. 23 4248–53
[34] Naguib M, Mochalin V N, Barsoum M W and Gogotsi Y 2014 25th anniversary article: MXenes: a new family of two-dimensional
materials Adv. Mater. 26 992–1005
[35] Simon P 2017 Two-dimensional MXene with controlled interlayer spacing for electrochemical energy storage ACS Nano 11 2393–6
[36] Yoshida M, Hoshiyama Y, Ommyoji J and Yamaguchi A 2010 Reaction mechanism for the synthesis of Ti3AlC2 through an
intermediate carbide of Ti3AlC from elemental Ti, Al, and C powder mixture J. Ceram. Soc. Japan 118 37–42
[37] Khoptiar Y, Gotman I and Gutmanas E Y 2005 Pressure-assisted combustion synthesis of dense layered Ti3AlC2 and its mechanical
properties J. Am. Ceram. Soc. 88 28–33
[38] Wang X H and Zhou Y C 2002 Microstructure and properties of Ti3AlC2 prepared by the solid–liquid reaction synthesis and
simultaneous in situ hot pressing process Acta Mater. 50 3143–51
[39] Han J-H, Hwang S-S, Lee D and Park S-W 2008 Synthesis and mechanical properties of Ti3AlC2 by hot pressing TiCx/Al powder
mixture J. Eur. Ceram. Soc. 28 979–88
[40] Hoffman E N, Yushin G, El-Raghy T, Gogotsi Y and Barsoum M W 2008 Micro and mesoporosity of carbon derived from ternary and
binary metal carbides Microporous Mesoporous Mater. 112 526–32
[41] Barsoum M W, El-raghy T, Farber L, Amer M, Christini R and Adams A 1999 The topotactic transformation of Ti3SiC2 into a partially
ordered cubic Ti (C 0. 67 Si 0. 06) phase by the diffusion of Si into molten cryolite J. Electrochem. Soc. 146 3919–23
[42] El-Raghy T, Barsoum M W and Sika M 2001 Reaction of Al with Ti3SiC2 in the 800–1000 °C temperature range Mater. Sci. Eng. A 298
174–8
[43] Seh Z W, Fredrickson K D, Anasori B, Kibsgaard J, Strickler A L, Lukatskaya M R, Gogotsi Y, Jaramillo T F and Vojvodic A 2016 Two-
dimensional molybdenum carbide (MXene) as an efficient electrocatalyst for hydrogen evolution ACS Energy Lett. 1 589–94
[44] Ma T Y, Cao J L, Jaroniec M and Qiao S Z 2016 Interacting carbon nitride and titanium carbide nanosheets for high-performance
oxygen evolution Angew. Chemie Int. Ed. 55 1138–42
[45] Gogotsi Y, Barsoum M W, Zhao M-Q, Ghidiu M and Lukatskaya M R 2014 Conductive two-dimensional titanium carbide ‘clay’ with
high volumetric capacitance Nature 516 1–9
[46] Khazaei M, Arai M, Sasaki T, Estili M and Sakka Y 2014 Two-dimensional molybdenum carbides: potential thermoelectric materials
of the MXene family Phys. Chem. Chem. Phys. 16 7841–9
[47] Xiao Y, Hwang J Y and Sun Y K 2016 Transition metal carbide-based materials: synthesis and applications in electrochemical energy
storage J. Mater. Chem. A 4 10379–93
[48] Kolesnikov A I, Lukatskaya M R, Gogotsi Y, Naguib M, Raymundo-Piñero E, Mashtalir O and Barsoum M W 2016 The effect of
hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene) Nanoscale 8 9128–33
[49] Mashtalir O, Naguib M, Mochalin V N, Dall’Agnese Y, Heon M, Barsoum M W and Gogotsi Y 2013 Intercalation and delamination of
layered carbides and carbonitrides Nat. Commun. 4 1716
[50] Malaki M, Maleki A and Varma R S 2019 MXenes and ultrasonication J. Mater. Chem. A 7 10843–57
[51] Chaudhari N K, Jin H, Kim B, Baek D S, Joo S H and Lee K 2017 MXene : an emerging two-dimensional material for future energy
J. Mater. Chem. A Mater. Energy Sustain. 00 1–16
[52] Naguib M, Dyatkin B, Presser V, Barsoum M W, Simon P, Gogotsi Y, Come J and Taberna P-L 2012 MXene: a promising transition
metal carbide anode for lithium-ion batteries Electrochem. Commun. 16 61–4
[53] Byeon A, Glushenkov A.M., Anasori B, Urbankowski P, Li J, Byles B.W., Blake B, Van Aken K.L., Kota S, Pomerantseva E, Lee J.W.,
Chen Y and Gogotsi Y 2016 Lithium-ion Capacitors with 2D Nb2CTx (MXene)–Carbon Nanotube Electrodes Journal of Power
Sources 326 686–94
[54] Ying G, Kota S, Dillon A D, Fafarman A T and Barsoum M W 2018 Conductive transparent V2CTx (MXene) films FlatChem 8 25–30
[55] Tang Q, Zhou Z and Shen P 2012 Are MXenes promising anode materials for li ion batteries? Computational studies on electronic
properties and Li storage capability of Ti3C2 and Ti3C2X2 (X=F, OH) monolayer J. Am. Chem. Soc. 134 16909–16
[56] Naguib M, Halim J, Lu J, Cook K M, Hultman L, Gogotsi Y and Barsoum M W 2013 New two-dimensional niobium and vanadium
carbides as promising materials for Li-ion batteries J. Am. Chem. Soc. 135 15966–9
[57] Goodenough J B and Park K-S 2013 The Li-ion rechargeable battery: a perspective J. Am. Chem. Soc. 135 1167–76
[58] Tarascon J-M 2010 Is lithium the new gold? Nat. Chem. 2 510–510
[59] Astruc D et al 2017 Recent advance in MXenes: a promising 2D material for catalysis, sensor and chemical adsorption Coord. Chem.
Rev. 352 306–27
[60] Wessells C D, Huggins R A and Cui Y 2011 Copper hexacyanoferrate battery electrodes with long cycle life and high power Nat.
Commun. 2 550
[61] Yoo H D, Shterenberg I, Gofer Y, Gershinsky G, Pour N and Aurbach D 2013 Mg rechargeable batteries: an on-going challenge Energy
Environ. Sci. 6 2265–79
[62] Li Q and Bjerrum N J 2003 Aluminum as anode for energy storage and conversion: a review Li, Q. and Bjerrum, N. J. Journal of Power
Sources, 2002, 110, (1), 1–10 Fuel Energy Abstr. 44 224
[63] Lukatskaya M R, Mashtalir O, Ren C E, Dall’Agnese Y, Rozier P, Taberna P L, Naguib M, Simon P, Barsoum M W and Gogotsi Y 2013
Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide Science (80-.) 341 1502–5

19
Mater. Res. Express 7 (2020) 022001 R Garg et al

[64] Wang X, Kajiyama S, Iinuma H and Hosono E 2012 Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid
capacitors Nature. Com 6 1–6
[65] Dall’Agnese Y, Taberna P-L, Gogotsi Y and Simon P 2015 Two-dimensional vanadium carbide (MXene) as positive electrode for
sodium-ion capacitors J. Phys. Chem. Lett. 6 2305–9
[66] Come J, Naguib M, Rozier P, Barsoum M W, Gogotsi Y, Taberna P-L, Morcrette M and Simon P 2012 A non-aqueous asymmetric cell
with a Ti2C-based two-dimensional negative electrode J. Electrochem. Soc. 159 A1368–73
[67] Zhou J, Zha X, Zhou X, Chen F, Gao G, Wang S, Shen C, Chen T, Zhi C and Eklund P 2017 Synthesis and electrochemical properties of
two-dimensional hafnium carbide ACS Nano 11 3841–50
[68] Bruce P G, Freunberger S A, Hardwick L J and Tarascon J-M 2012 Erratum: Li–O2 and Li–S batteries with high energy storage Nat.
Mater. 11 172–172
[69] Li W, Zhang Q, Zheng G, Seh Z W, Yao H and Cui Y 2013 Understanding the role of different conductive polymers in improving the
nanostructured sulfur cathode performance Nano Lett. 13 5534–40
[70] Zhao Y and Zhao J 2017 Functional group-dependent anchoring effect of titanium carbide-based MXenes for lithium-sulfur batteries:
a computational study Appl. Surf. Sci. 412 591–8
[71] Liang X, Garsuch A and Nazar L F 2015 Sulfur cathodes based on conductive mxene nanosheets for high-performance lithium-sulfur
batteries Angew. Chemie Int. Ed. 54 3907–11
[72] Frost R L, Kristof J, Horvath E, Martens W N and Kloprogge J T 2002 Complexity of intercalation of hydrazine into kaolinite—a
controlled rate thermal analysis and DRIFT spectroscopic study J. Colloid Interface Sci. 251 350–9
[73] Deng Y, Dixon J B and White G N 2003 Molecular configurations and orientations of hydrazine between structural layers of kaolinite
J. Colloid Interface Sci. 257 208–27
[74] Kajiyama S, Szabova L, Sodeyama K, Iinuma H, Morita R, Gotoh K, Tateyama Y, Okubo M and Yamada A 2016 Sodium-ion
intercalation mechanism in MXene nanosheets ACS Nano 10 3334–41
[75] Osti N C, Naguib M, Ganeshan K, Shin Y K, Ostadhossein A, van Duin A C T, Cheng Y, Daemen L L, Gogotsi Y and Mamontov E 2017
Influence of metal ions intercalation on the vibrational dynamics of water confined between MXene layers Phys. Rev. Mater. 1 65406
[76] Come J, Black J M, Lukatskaya M R, Naguib M, Beidaghi M, Rondinone A J, Kalinin S V, Wesolowski D J, Gogotsi Y and Balke N 2015
Controlling the actuation properties of MXene paper electrodes upon cation intercalation Nano Energy 17 27–35
[77] Ganguly A 2012 Fundamentals of Inorganic Chemistry (India: Pearson Education)
[78] Levi M D, Sigalov S, Salitra G, Elazari R and Aurbach D 2011 Assessing the solvation numbers of electrolytic ions confined in carbon
nanopores under dynamic charging conditions J. Phys. Chem. Lett. 2 120–4
[79] Byeon A, Zhao M-Q, Ren C E, Halim J, Kota S, Urbankowski P, Anasori B, Barsoum M W and Gogotsi Y 2017 Two-dimensional
titanium carbide MXene as a cathode material for hybrid magnesium/lithium-ion batteries ACS Appl. Mater. Interfaces 9 4296–300
[80] Zhao M-Q, Ren C E, Alhabeb M, Anasori B, Barsoum M W and Gogotsi Y 2019 Magnesium-ion storage capability of MXenes ACS
Appl. Energy Mater. 2 1572–8
[81] Li J, Yuan X, Lin C, Yang Y, Xu L, Du X, Xie J, Lin J and Sun J 2017 Achieving high pseudocapacitance of 2D titanium carbide (MXene)
by cation intercalation and surface modification Adv. Energy Mater. 7 1602725
[82] Yu Y-X 2016 Prediction of mobility, enhanced storage capacity, and volume change during sodiation on interlayer-expanded
functionalized Ti3C2 MXene anode materials for sodium-ion batteries J. Phys. Chem. C 120 5288–96
[83] Ghidiu M, Halim J, Kota S, Bish D, Gogotsi Y and Barsoum M W 2016 Ion-exchange and cation solvation reactions in Ti3C2 MXene
Chem. Mater. 28 3507–14
[84] Luo J, Zhang W, Yuan H, Jin C, Zhang L, Huang H, Liang C, Xia Y, Zhang J and Gan Y 2017 Pillared structure design of MXene with
ultralarge interlayer spacing for high-performance lithium-ion capacitors ACS Nano 11 2459–69
[85] Wang L, Dong Z H, Wang Z G, Zhang F X and Jin J 2013 Layered α-Co (OH) 2 Nanocones as electrode materials for Pseudocapacitors:
understanding the effect of interlayer space on electrochemical activity Adv. Funct. Mater. 23 2758–64
[86] Wang H-W, Hu Z-A, Chang Y-Q, Chen Y-L, Wu H-Y, Zhang Z-Y and Yang Y-Y 2011 Design and synthesis of NiCo2O4–reduced
graphene oxide composites for high performance supercapacitors J. Mater. Chem. 21 10504–11
[87] Kurra N, Ahmed B, Gogotsi Y and Alshareef H N 2016 Mxene-on-paper coplanar microsupercapacitors Adv. Energy Mater. 6 1601372
[88] Boota M, Anasori B, Voigt C, Zhao M-Q, Barsoum M W and Gogotsi Y 2016 Pseudocapacitive electrodes produced by oxidant-free
polymerization of pyrrole between the layers of 2D titanium carbide (MXene) Adv. Mater. 28 1517–22
[89] Ling Z, Ren C E, Zhao M-Q, Yang J, Giammarco J M, Qiu J, Barsoum M W and Gogotsi Y 2014 Flexible and conductive MXene films
and nanocomposites with high capacitance Proc. Natl Acad. Sci. 111 16676–81
[90] Peng Y-Y, Akuzum B, Kurra N, Zhao M-Q, Alhabeb M, Anasori B, Kumbur E C, Alshareef H N, Ger M-D and Gogotsi Y 2016 All-
MXene (2D titanium carbide) solid-state microsupercapacitors for on-chip energy storage Energy Environ. Sci. 9 2847–54
[91] Xie Y, Naguib M, Mochalin V N, Barsoum M W, Gogotsi Y, Yu X, Nam K-W, Yang X-Q, Kolesnikov A I and Kent P R C 2014 Role of
surface structure on li-ion energy storage capacity of two-dimensional transition-metal carbides J. Am. Chem. Soc. 136 6385–94
[92] Snook G A, Kao P and Best A S 2011 Conducting-polymer-based supercapacitor devices and electrodes J. Power Sources 196 1–12
[93] Ren C E, Zhao M-Q, Makaryan T, Halim J, Boota M, Kota S, Anasori B, Barsoum M W and Gogotsi Y 2016 Porous two-dimensional
transition metal carbide (MXene) flakes for high-performance Li-Ion storage ChemElectroChem 3 689–93
[94] Qin L, Tao Q, El Ghazaly A, Fernandez-Rodriguez J, Persson P O Å, Rosen J and Zhang F 2017 High-performance ultrathin flexible
solid-state supercapacitors based on solution processable Mo 1.33 C MXene and PEDOT:PSS Adv. Funct. Mater. 28 11–27
[95] Come J et al 2012 Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors Nat. Commun. 6 1–6
[96] Xu S, Liu W, Liu X, Kuang X and Wang X 2017 A MXene based all-solid-state microsupercapacitor with 3D interdigital electrode 2017
19th Int. Conf. on Solid-State Sensors, Actuators and Microsystems (TRANSDUCERS) ((IEEE)) pp 706–709
[97] Rakhi R B, Ahmed B, Anjum D and Alshareef H N 2016 Direct chemical synthesis of MnO2 nanowhiskers on transition-metal carbide
surfaces for supercapacitor applications ACS Appl. Mater. Interfaces 8 18806–14
[98] Xia Q X, Fu J, Yun J M, Mane R S and Kim K H 2017 High volumetric energy density annealed-MXene-nickel oxide/MXene
asymmetric supercapacitor RSC Adv. 7 11000–11
[99] Boota M, Pasini M, Galeotti F, Porzio W, Zhao M-Q, Halim J and Gogotsi Y 2017 Interaction of polar and nonpolar polyfluorenes
with layers of two-dimensional titanium carbide (MXene): intercalation and pseudocapacitance Chem. Mater. 29 2731–8
[100] Wen Y, Rufford T E, Chen X, Li N, Lyu M, Dai L and Wang L 2017 Nitrogen-doped Ti3C2Tx MXene electrodes for high-performance
supercapacitors Nano Energy 38 368–76
[101] Dall’Agnese Y, Lukatskaya M R, Cook K M, Taberna P L, Gogotsi Y and Simon P 2014 High capacitance of surface-modified 2D
titanium carbide in acidic electrolyte Electrochem. Commun. 48 118–22

20
Mater. Res. Express 7 (2020) 022001 R Garg et al

[102] Li L, Zhang N, Zhang M, Wu L, Zhang X and Zhang Z 2018 Ag-nanoparticle-decorated 2D titanium carbide (MXene) with superior
electrochemical performance for supercapacitors ACS Sustain. Chem. Eng. 6 7442–50
[103] Hu Z, Zhu Z, Cheng F, Zhang K, Wang J, Chen C and Chen J 2015 Pyrite FeS2 for high-rate and long-life rechargeable sodium
batteries Energy Environ. Sci. 8 1309–16
[104] Liu T, Kim K C, Kavian R, Jang S S and Lee S W 2015 High-density lithium-ion energy storage utilizing the surface redox reactions in
folded graphene films Chem. Mater. 27 3291–8
[105] Mahmood Q, Park S K, Kwon K D, Chang S, Hong J, Shen G, Jung Y M, Park T J, Khang S W and Kim W S 2016 Transition from
diffusion-controlled intercalation into extrinsically pseudocapacitive charge storage of MoS2 by nanoscale heterostructuring Adv.
Energy Mater. 6 1501115
[106] Zhang Q, Wang X, Pan Z, Sun J, Zhao J, Zhang J, Zhang C, Tang L, Luo J and Song B 2017 Wrapping aligned carbon nanotube
composite sheets around vanadium nitride nanowire arrays for asymmetric coaxial fiber-shaped supercapacitors with ultrahigh
energy density Nano Lett. 17 2719–26

21