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Achieving High Pseudocapacitance of 2D Titanium Carbide

Full paper
(MXene) by Cation Intercalation and Surface Modification
Jian Li, Xiaotao Yuan, Cong Lin, Yanquan Yang, Le Xu, Xin Du, Jinglin Xie, Jianhua Lin,*
and Junliang Sun*

chemical performance and even with a

Supercapacitors attract great interest because of the increasing and urgent theoretical EDLC of ≈550 F g−1 as a very
demand for environment-friendly high-power energy sources. Ti3C2, a member large surface area of 2180–3100 m2 g−1,[3–7]
of MXene family, is a promising electrode material for supercapacitors owing but the specific capacitance was ≈300 F g−1
in practice and far from wide applications.
to its excellent chemical and physical properties. However, the highest
Recently, an N-doped ordered mesoporous
gravimetric capacitance of the MXene-based electrodes is still relatively low carbon has a capacitance of 855 F g−1 by
(245 F g−1) and the key challenge to improve this is to exploit more pseudo- enabling redox reactions, which makes
capacitance by increasing the active site concentration. Here, a method to this carbon material possible for energy
significantly improve the gravimetric capacitance of Ti3C2Tx MXenes by cation storage.[8] So using pseudocapacitive mate-
intercalation and surface modification is reported. After K+ intercalation and rials is a way to increase gravimetric capac-
itances. As pseudocapacitive materials,
terminal groups (OH−/F−) removing , the intercalation pseudocapacitance
some transitional metal oxides (MnO2,[1,9]
is three times higher than the pristine MXene, and MXene sheets exhibit a Co3O4,[10] etc.) provide higher capacitance
significant enhancement (about 211% of the origin) in the gravimetric capaci- and energy densities, but always suffer
tance (517 F g−1 at a discharge rate of 1 A g−1). Moreover, the as-prepared from short life cycles. Hydrated ruthe-
electrodes show above 99% retention over 10 000 cycles. This improved elec- nium oxide, RuO2, can achieve impressive
capacitance (600 F g−1) and long life cycles,
trochemical performance is attributed to the large interlayer voids of Ti3C2 and
but its high price limits its widely spread
lowest terminated surface group concentration. This study demonstrates a applications.[11]
new strategy applicable to other MXenes (Ti2CTx, Nb2CTx, etc.) in maximizing In recent years, MXenes, a new large
their potential applications in energy storage. family of 2D materials, have received sig-
nificant research interests as electrode
materials for their excellent electrochem-
1. Introduction ical energy storage properties[12–21] and good electrical conduc-
tivity.[22–24] MXenes have the general composition of Mn+1XnTx,
Supercapacitors, possessing higher power densities than bat- where M is an early transition metal, X can be carbon (C) or
teries and higher energy densities than conventional dielectric nitrogen (N), and n = 1, 2, 3, and Tx represents surface func-
capacitors, are considered as the next generation energy storage tional groups (O, OH, and F). MXenes can be produced
devices.[1] Among various electrode materials available for super­ by etching out the A layers (mostly group 13 and 14 elements)
capacitors, 2D solids have attracted great interest because of from MAX phases.[25–29] So far, more than 70 different pure
their large electrochemical active surface.[2] Although graphene MAX phases are reported.[3,25,26,28] Because of the differences
is the most well-known layered material, electrical double-layer in character and relative strengths of M–A compared with the
capacitance (EDLC) is the major proportion of capacitance for MX bonds, the A layers can be selectively removed by chemi-
intrinsic graphene with less edges and defects. Without redox cals, such as hydrofluoric acid (HF),[16,23,30] NH4HF2, or acidic
reactions (pseudocapacitance), graphene has limited electro- solution of fluoride salts, such as LiF in HCl.[12] In this pro-
cess, the Al atoms are replaced by O, OH, and/or F ter-
minal groups. Hence, they can be represented as Mn+1XnTx. The
removal of the Al layers dramatically weakens the interactions
J. Li, X. Yuan, C. Lin, Y. Yang, Dr. L. Xu, between the Mn+1Xn layers, which, in turn, allows them to be
X. Du, Prof. J. Xie, Prof. J. Lin, Prof. J. Sun readily separated by shear or any similar mechanical methods
College of Chemistry and Molecular Engineering
Peking University like other layered materials, such as graphite and transitional
Yiheyuan Road 5, Beijing 100871, China metal sulfides (TMDs).[6,31,32] The exfoliated carbides or car-
E-mail: junliang.sun@pku.edu.cn; jhlin@pku.edu.cn bonitrides exhibit structural similarity to exfoliated graphite and
C. Lin hence are termed as MXenes.
College of Chemistry and Chemical Engineering It was reported that the energy storage capacities of MXenes
Chongqing University
NO.174, Shazheng Street, Shapingba District, Chongqing 400044, China
were found to strongly depend on the nature of surface ter-
minal groups by a combination of density functional theory
DOI: 10.1002/aenm.201602725 (DFT) calculations and experiments.[17] The surface termination

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of F and OH blocks electrolyte ion transport and decreases terminated with OH and F groups. As TiF bonds become
Full paper

energy storage capacity[20] and 245 F g−1 is the highest gravi-
metric capacitance for pristine MXene film to date.[12] In a
recent report, Gogotsi and co-workers revealed the mechanism
of capacitance in Ti3C2Tx MXene by in situ X-ray absorption
spectroscopy (XAS) combined with electrochemical experi-
ments, where the pseudocapacitance of Ti3C2Tx MXene was
originated from the redox reactions of Ti atoms.[33] They found
that an increase in the interlayer spacing of Ti3C2Tx facilitates
the charge transport in supercapacitor electrodes[14] and lower
terminated group concentration on the surface leads to more
Ti atoms participating in redox reactions. Hence, the potential
of MXenes in energy storage can be maximized by modifying
structure and surface termination of MXenes. Here, we report
a method to significantly improve the specific capacitance of
Ti3C2Tx MXene by cation intercalation and surface modifica-
tion. Together with their excellent stabilities, a high energy den-
sity of 27.4 W h kg−1 makes MXenes a promising pseudocapaci-
tance electrode material in real applications.
2. Results and Discussion
2.1. Sample Preparation and Surface Studies
The synthesis of the cation intercalation and surface group
modified Ti3C2Tx MXene sheets is summarized in Figure 1a
briefly. In the first step, Al was selectively etched from Ti3AlC2
to produce the sample called Ti3C2Tx whose layer surfaces were
unstable at basic solution and MXene prefers to intercalate cat-
ions,[16,17] the large radius cation base, KOH, was selected as the
reagent for replacing F terminal groups with hydroxyl groups
and intercalating K+ ions between 2D Ti3C2 MXene spontane-
ously, which generates the sample called KOH-Ti3C2. The sam-
ples Ti3C2Tx and KOH-Ti3C2 were calcined under 673 K in the
Ar atmosphere to modify the surface terminal groups, which
generates the samples 400-Ti3C2Tx and 400-KOH-Ti3C2, respec-
tively. To study the cation size effect, the Ti3C2Tx MXene sheets
were also treated by other bases with different cation radius
(NH4OH, LiOH, NaOH) under the similar conditions and the
corresponding samples were named as 400-NH4OH-Ti3C2,
400-LiOH-Ti3C2, and 400-NaOH-Ti3C2.
Fluorine and oxygen were clearly observed in X-ray photo-
electron spectroscopy (XPS), combined with energy-dispersive
spectroscopy (EDS) (Figures S3a, S4a,b, S5a, and S6a, Sup-
porting Information), showing the formation of TiF and
TiO bonds after Al removal. X-ray diffraction (XRD) revealed
that the (00l) peak in the etched material is broadened and shifted
to a lower 2θ angle, indicating larger interlayer distance in the
HF etched sample (Figure 1b). After the treatment by KOH,
the intensity of the TiF peaks decreases quickly (Figure S4a,
Supporting Information) and the contents of OH on the sur-
face increased significantly in XPS analysis (Figures S3c and
S4b, Supporting Information), indicating that large amount of
F terminal groups was replaced by hydroxyl groups. In the
meantime, the KOH treatment further increased the c-lattice
parameter from 19.2 to 25.0 Å (Figure 1b), indicating even

Figure 1. Schematic of the modified MXene. a) Schematic of modified MXenes synthesis. b) XRD patterns of different samples. The (00l) peaks for
K+ intercalated samples are located at much lower angles than that of Ti3C2Tx, while the (110) peak is at the similar position, showing the intact layers
with increased interlayer distances. c) SEM and d) TEM images of Ti3C2Tx. e) SEM and f) TEM images of 400-KOH-Ti3C2.

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larger interlayer distances of KOH-Ti3C2 (from 9.6 to 12.5 Å).
The samples treated by other bases with different cations
(NH4OH, LiOH, NaOH) also have the similar 002 peak posi-
tions with their interlayer distances about 12.7, 12.6, and 12.4
Å, respectively (Figure S7a, Supporting Information). The sim-
ilar interlayer distances may be due to the different degree of
cation solvation and the presence of water between Ti3C2 layers
which minimizes the cation size effects.[34]
After calcination at 673 K, the samples 400-Ti3C2Tx and
400-KOH-Ti3C2 exhibit the same interlayer distances to their
own original Ti3C2Tx and KOH-Ti3C2, while the effective inter-
layer voids actually increased from 4.8 to 7.7 Å where many
terminal groups were removed in 400-KOH-Ti3C2 (Figure 1a;
the method to calculate the interlayer voids is shown in the
Supporting Information and Figure S2e, Supporting Informa-
tion), which may benefit the electrochemical performance as
discussed later. For other samples, the calcination decreased
the interlayer distances quite significantly to about 12.2, 10.5,
and 10.2 Å for 400-NaOH-Ti3C2, 400-LiOH-Ti3C2, and400-
NH4OH-Ti3C2, respectively, indicating that the degree of
cation solvation was decreasing and the water between Ti3C2
layers was removed after calcination (Figure S7b, Supporting
Information). Thus, the cation size does not have influence on
the interlayer distance of the bases treated samples but has a
significant influence on the interlayer voids after calcination.
Note that 400-Ti3C2Tx and 400-KOH-Ti3C2 contain a small
amount of anatase TiO2, which was produced by the local
overheating during calcination. The EDS (Figure S5a–d, Sup-
porting Information) shows that the ratio between Ti and C
are all close to 1.5 for 400-Ti3C2Tx, KOH-Ti3C2, and 400-KOH-
Ti3C2, indicating that the Ti3C2 MXene layer was not destroyed
after being treated by KOH or calcination. The carbon content
in Ti3C2Tx (Figure S5a, Supporting Information) was higher
than other samples, and the possible reason is that there was
some amorphous carbon formed during the HF etching. But
after being treated by KOH (Figure S5c, Supporting Infor-
mation) or calcination at 673 K (Figure S5b,d, Supporting
Information), the amorphous carbon was removed. The EDS
elemental mapping of Ti and K confirmed that potassium is
present homogeneously in all MXene sheets in KOH-Ti3C2
and 400-KOH-Ti3C2 (shown in Figure S6c,d, Supporting
Information). Shown by scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) images
in Figure 1c–f and Figure S8a–d (Supporting Information),
Ti3C2Tx was the stacking of MXene sheets resembling exfoli-
ated graphite and there is no visible change in the morphology
after the KOH treatment or calcination. Moreover, rotation
electron diffraction (RED) data of 400-KOH-Ti3C2 were col-
lected and its reconstructed 3D reciprocal space showed that a
series of streaks along the c*-axis form a hexagonal pattern in
the a*–b* plane (Figure S8e,f, Supporting Information), con-
firming that the Ti3C2 layer structure was retained but with a
small thickness or stacking disorder after the KOH treatment
and calcination.[35]
The surface structure is crucial for the electrochemical per-
formance and thus several different techniques were applied
for the prepared samples. Thermogravimetric-differential scan-
ning calorimetry-mass spectrometry (TG-DSC-MS) analysis of
MXene sheets was carried out in situ to track the releasing of
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terminal groups during calcination (Figure 2a,b). The TG-MS
Full paper
result for Ti3C2Tx shows that the weight loss of 4.56% from
373 to 663 K could be assigned as OH, H2O, F, HF, and
CO2 species. From MS analysis, there were two releasing OH
(H2O) peaks with m/z = 17 (18) (from room temperature (RT)
to 473 K and from 473 to 673 K), which can be attributed to
the absorbed water and the terminal OH on MXene layer sur-
face. The peak with m = 19, 20 which occurred in the range of
473–623 K, could be attributed to terminal F on MXene layer
surfaces. It suggests that many terminal F and OH were
removed after the calcination under 673 K shown in Figure S3b
(Supporting Information). After the KOH treatment, KOH-
Ti3C2 has a similar weight loss of 5.01% below 673 K and the
major difference is that there is no visible F/HF release at
m = 19, 20. This difference indicates that the fluorine concen-
tration of MXene materials decreased significantly during the
KOH treatment as the amount of F terminal groups was
replaced by hydroxyl groups. From MS analysis, there is some
CO2 releasing with m = 44 over 500 K, which was from the par-
tial decomposition of MXene caused by the local overheating
during calcination. To further confirm the release of OH ter-
minals by calcination under 673 K, the degassing Fourier trans-
form infrared (FTIR) measurement was carried out for KOH-
Ti3C2 and 400-KOH-Ti3C2 samples (Figure 2c). The comparison
of these two spectra clearly showed the disappearance of the
broadband around 3600 cm−1, suggesting that the terminal
OH could be efficiently removed by calcination under 673 K
in Ar.
The Brunner−Emmet−Teller (BET) surface area calculated
for Ti3AlC2, Ti3C2Tx, KOH-Ti3C2, 400-Ti3C2Tx, and 400-KOH-
Ti3C2 are 1.4, 9.2, 13.0, 20.5, and 22.6 m2 g−1, respectively
(Figure 2d). A small increase of the surface area in this order
is mainly due to the increasing of the interlayer spacing after
different treatments, suggesting removal of terminal groups
from the sample. Note that not all interlayer voids are acces-
sible for Ar due to the small voids and the presence of residue
O and K between layers. Although the largest surface area
is still relatively small compared with carbon materials, this
increase may significantly increase the ion diffusion or active
site accessibilities. Note that all the calcined samples have a
larger distinct hysteresis loops in the range of 0.30–1.0 P/P0,
which suggests the presence of mesopores between layers
which is also shown in Figure 1c–e and Figure S8 (Supporting
Information).
By summarizing the above results, schematic surface struc-
ture models can be built for different samples as shown in
Figure 1a. The MAX phase Ti3AlC2 is transformed to the MXene
Ti3C2Tx nanosheets by the hydrofluoric acid treatment. Ti3C2Tx
exhibits expansion of the interlayer distance by K+ intercala-
tion. The XRD results showed that the interlayer distance for
Ti3C2Tx and KOH-Ti3C2 were not changed before/after the heat
treatment. The TG-DSC-MS data indicated that some terminal
group (OH or F) were removed during calcination, and the
EDS and XPS analysis showed that most of the terminal group
but not all were removed after calcination. So it was the residue
O terminal together with the K ions which kept the interlayer
distance constant and increased the effective interlayer voids
significantly after calcination, resulting in better accessibility of
the active sites as discussed later.
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Figure 2. Surface studies of MXene. TG-DSC-MS analysis of a) Ti3C2Tx and b) KOH-Ti3C2. The fragments with different m values 17, 18, 19, 20, and 44
could be attributed to OH, H2O, F, HF, and CO2, respectively. Both samples have two releasing stage for OH/H2O, contributed by the absorbed
water and terminal OH groups, respectively. The disappearance of F/HF for the KOH-Ti3C2 sample indicated that F terminals were removed by
the KOH treatment. c) Degassing FTIR measurement of Ti3C2Tx, KOH-Ti3C2, and 400-KOH-Ti3C2. The degassing FTIR measurement showed the disap-
pearance of the stretching vibration of OH groups (the broadband around 3600 cm−1) for 400-KOH-Ti3C2, suggesting that the terminal OH could
be efficiently removed after calcination. d) Ar adsorption and desorption isotherms. This small increase is consistent with the stacking structure where
the interlayer voids are not accessible for the Ar gas.

2.2. Electrochemical Properties
To evaluate the electrochemical performance of the Ti3C2Tx,
KOH-treated MXene (KOH-Ti3C2), and investigate the possible
influence of removing of terminal OH and F (400-Ti3C2Tx,
400-KOH-Ti3C2) on the electrochemical performance, we con-
ducted cyclic voltammetry (CV) and galvanostatic charge–dis-
charge (CC) experiments in the three-electrode system and
symmetric two-electrode configurations. A series of pre-exper-
iments were performed to select a suitable potential range and
ensure the electrochemical behavior is not due to electrolyte
decomposing (Figure S9, Supporting Information). Ultimately,
the potential range was selected until there is no noticeable gas
evolution.
Figure 3 depicts the electrochemical performances of the
different MXene electrodes measured in the three-electrode
system. The CVs were conducted in the potential range of
−0.1 to 0.4 V for Ti3C2Tx and KOH-Ti3C2 and −0.2 to 0.4 V for
400-Ti3C2Tx and 400-KOH-Ti3C2. For the same mass loading,
the CV curves show different areas indicating different levels
of stored charges. From the CV loops, the specific capacitances
of 244 and 348 F g−1 at a scan rate of 1 mV s−1 are obtained for
Ti3C2Tx and KOH-Ti3C2, respectively (Figure 3a and Figure S10,
Supporting Information). The pristine Ti3C2Tx material yielded
a similar capacitance to those in the previous reports,[12] while
the capacitance of KOH-Ti3C2 is much higher than that of
Ti3C2Tx. This enhancement in capacitance most likely origi-
nated from the two times larger interlayer distances (Figure 1a)
in the KOH-Ti3C2 than in Ti3C2Tx and lower F concentration
on the MXene layer surface. As mentioned above, the interlayer
distance of Ti3C2Tx increased from 9.6 to 12.5 Å after KOH
treatment, which facilitates the electrolyte ionic diffusion.
After removing most terminal groups by calcination at 673 K,
400-KOH-Ti3C2 yielded the highest capacitance of 500 F g−1 (at
scan of 1 mV s−1, shown in Figure 3a) or 517 F g−1 (at a dis-
charge rate of 1 A g−1, shown in Figure 3b). Compared with
KOH-Ti3C2, a sharp rise in capacitance was observed. This can
be ascribed to the more accessible active sites in 400-KOH-Ti3C2
due to the removal of much terminal groups after calcination
(Figure 1a). To our best knowledge, a gravimetric capacitance

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Full paper
Figure 3. Electrochemical performance of MXene and surface modified MXene electrodes in three-electrode system. a) Cycle voltammetry profiles at
1 mV s−1 for different MXene-based electrodes in 1 m H2SO4. b) The galvanostatic charge/discharge curves for 400-KOH -Ti3C2 MXene sheets at current
densities of 1, 2, 5, and 10 A g−1. c) Cyclic voltammetry profiles at 10 mV s−1 for other cation intercalation MXene sheets with lowest terminal groups.
d) Comparison of capacitance for MXene sheets (at scan rate of 1 mV s−1). The total capacitance is separated into intercalation pseudocapacity and
surface capacitive contributions (the inset numbers 104, 120, 168, and 304 point to the part of intercalation pseudocapacity). e) Capacitance retention
test of 400-KOH-Ti3C2 electrode in 1 m H2SO4 (the blue lines were error bars). Inset shows galvanostatic cycling data collected 1 A g−1. f) Electrochemical
impedance spectroscopy data of different MXene-based electrodes. The inset in (f) shows the magnified high-frequency region.

of 517 F g−1 is the highest value reported for MXene-based
electrodes to date and it has 211% enhancement of capaci-
tance compared with the previous reported highest value. The
CV curves of other cation intercalated MXene sheets with
the lowest terminal group concentration (400-NH4OH-Ti3C2,
400-LiOH-Ti3C2, 400-NaOH-Ti3C2) are shown in Figure 3c. It
was clear that the supercapacitor performance increased with
the increasing interlayer voids of MXene sheets. In order to
confirm the origin of enhanced performance of 400-KOH-
Ti3C2Tx from the more accessible active sites (Ti atoms), ex situ
XPS was done to reveal the redox reaction of Ti during its elec-
trochemical cycling. As shown in Figure S11 (Supporting Infor-
mation), there is a clear change of binding energy of Tix+2p3/2
and Tiy+2p3/2 at different potentials. And we can see that the
average oxidation state of Ti changes wider for 400-KOH-Ti3C2
than that for Ti3C2Tx over a 0.6 V window.
A comparison of the rate performance of all the samples is
presented in Figure S12 (Supporting Information). A decline in
capacitance at higher scan rates was noticed, which was common
for pseudocapacitive electrodes since the rate of electrochemical
reaction was controlled by electrolyte ion diffusion at high scan
rates. In general, the capacitance C on the basis of CV experiment
may contain a rate-independent component k1 (surface capacitive
effects: EDLC and pseudocapacitance), and a diffusion-limited
component controlled by the scanning rate (ν) (intercalation-
pseudocapacitance), taking the form as previously reported[36,37]
C = i(V )/ν = k1 + k2ν −0.5
As shown in Figure S13 (Supporting Information), at scan
rates above 20 mV s−1, the response is not diffusion-controlled
but is rather due to surface capacitive effects (EDLC and pseu-
docapacitive). But when the scan rates were below 20 mV s−1,
there is a noticeable contribution from diffusion-limited pro-
cesses (intercalation-pseudocapacitance). In particular, at the
rate of 1 mV s−1, the intercalation-pseudocapacitance (Figure 3d)
contributed 42%, 43%, 48%, and 62% of the total capacitances
for Ti3C2Tx, 400-Ti3C2Tx, KOH-Ti3C2, and 400-KOH-Ti3C2,
respectively. Clearly, the intercalation-pseudocapacitance con-
tributions from 400-KOH-Ti3C2 (304 F g−1) are significantly
higher (almost three times) than pristine Ti3C2Tx (104 F g−1). It
can be attributed to the better accessibility of the active sites (Ti
atoms) by the electrolyte after K+ intercalation and calcination.
To further confirm the effects of cation diffusion, the influence
of cation radius in electrolyte was also investigated (shown in
Figure S14, Supporting Information). The specific capacitances
decease in the order of H2SO4, Li2SO4, Na2SO4, and K2SO4 at
the same scan rate of 10 mV s−1. This suggests that the H+ as
the smallest cation can be intercalated into MXene layers faster
and easier for surface redox reaction, which results in more
contributions to intercalation-pseudocapacitance in the same
scan rate.
The galvanostatic charge/discharge curves for 400-KOH-
Ti3C2 MXene sheets at current densities of 1, 2, 5, and 10 A g−1
confirmed high reversibility of the redox reactions (shown in
Figure 3b). The other samples of MXene sheets showed similar
behavior as that of 400-KOH-Ti3C2 (shown in Figure S15, Sup-
porting Information). The 400-KOH-Ti3C2 MXene electrodes
(1) withstood 10 000 cycles with above 99% of the capacitance
remaining, confirming that such high columbic efficiency was
not due to decomposing electrolyte or other parasitic reactions
(shown in Figure 3e). Electrochemical impedance spectroscopy

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Full paper

the same electrolyte. At a high power den-

Figure 4. Electrochemical performance of 400-KOH-Ti3C2 in the three-electrode system.
a) Comparison of rate performances reported in this work and previously for Ti3C2Tx[15,16,21] and than the theoretical decomposition potential
Ti2CTx electrodes.[12] b) Power density versus energy density plot of 400-KOH-Ti3C2 and previ- of water (1.23 V). Figure S16 (Supporting
ously reported Ti3C2Tx electrodes.[12,16]
was further performed to study the charge transfer resistance
(Rct) and ion transport in the tested electrodes (Figure 3f).
Nyquist plots of all samples showed negligible semicircles and
a relative low Rct, suggesting that removing the terminal group
did not significantly affect the electronic conductivity of Ti3C2Tx
and KOH-Ti3C2. In the low frequency range, Nyquist plots for
both Ti3C2Tx and KOH-Ti3C2 electrodes reflect a good ionic con-
ductivity of the electrodes. At high frequencies, the slope of the
plot for 400-Ti3C2Tx and 400-KOH-Ti3C2 shows a slightly lower
diffusion resistance compared to the sample with terminal
groups. This may be caused by the lower concentration of sur-
face terminal groups after calcination.
A comparison of the rate performance of the 400-KOH-Ti3C2
electrodes with previously reported Ti3C2Tx and Ti2CTx elec-
trodes is shown in Figure 4a,b. The gravimetric capacitance
from CV of the 400-KOH-Ti3C2 electrode is significantly higher
than that of reported Ti3C2Tx and Ti2CTx electrodes because of
the larger interlayer voids and lowest terminal group concentra-
tion. The energy (E) and power densities (P) for the 400-KOH-
Ti3C2 electrodes were calculated from CV curves at different
scan rates (shown in Figure 4b). At the scan rate of 2 mV s−1,
the 400-KOH-Ti3C2 electrodes have a specific energy density E
−1
of 23.6 W h kg based on the weight of active material, which
was 2.3 times higher than that of reported Ti3C2Tx clay[12] in
sity of 6.39 kW kg−1 (at the scan rate of
100 mV s−1), the energy density obtained for
400-KOH-Ti3C2 electrodes is 10.65 W h kg−1.
As the pseudocapacitance was shown to origi-
nate mostly from redox reactions of the Ti
atoms,[33] it was not surprising that the capac-
itance of 400-KOH-Ti3C2 decreased at higher
scan rates.
Figure 5 shows the electrochemical per-
formances of the symmetric 400-KOH-
Ti3C2//400-KOH-Ti3C2 supercapacitor. Most
interesting and extraordinary finding is
that these symmetric supercapacitors could
operate at potentials of 1.6 V which is larger
Information) depicts the cyclic voltammo-
grams at the potential range from 1.0 to
1.6 V. It is clear that there was no obvious electrolyte decompo-
sition peak below 1.6 V, but the shapes of CV curves (in terms
of the existence of redox peak and its position) were different,
the possible reason was that it presents a continuous change in
the titanium oxidation state[33] and the state of residue terminal
group during charge/discharge. The Ragone plots of the super-
capacitors in Figure 5b show that the symmetric supercapacitor
exhibited a maximal energy density of 27.4 W h kg−1 at the cur-
rent density of 1 A g−1 when the operated potential was at 1.6 V.
Even at a high power density of 4.0 kW kg−1, the energy density
still remains 17.1 W h kg−1. Given the potential window for two-
electrode symmetric device was more than two times compared
with one electrode, we further evaluated its long-term stability
by life cycle test in mixed solution of 1 m H2SO4 and 1 m Li2SO4
up to 5000 cycles at the discharging rate of 1 A g−1. The capaci-
tance retention was 90.4% (Figure 5c). It is evident that cation
intercalation combined with surface group modification is an
effective strategy for maximizing the performance of MXene
sheets as a promising pseudocapacitance electrode material.
3. Conclusions
In summary, we have demonstrated that cation intercalation
and surface group modification of 2D Ti3C2Tx MXenes show

Figure 5. Electrochemical performance of the symmetric 400-KOH-Ti3C2//400-KOH-Ti3C2 supercapacitor in 1 m H2SO4. a) Cyclic voltammetry (CV)
profiles at different scan rates under the potential of 1.6 V. b) Power density versus energy density plot of the symmetric supercapacitor at different
potential by CV test and galvanostatic charge–discharge (CC) test. c) Life cycle test in mixed solution of 1 m H2SO4 and 1 m Li2SO4 up to 5000 cycles
at the discharging rate of 1 A g−1.

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a significant enhancement in the gravimetric capacitance per-
formance (mainly intercalation pseudocapacitance) compared
with pristine Ti3C2Tx electrodes. After K+ ion intercalation and
calcination, the MXene sample exhibited high performance
with specific capacitance over 500 F g−1 at 1 mV s−1, and excel-
lent cycling stability (above 99% remain after 10 000 cycles)
when used in three-electrode configuration in 1 m H2SO4. The
symmetric supercapacitor exhibited a maximal energy den-
sity of 27.4 W h kg−1 in mixed solution of 1 m H2SO4 and 1 m
Li2SO4 at the current density of 1 A g−1, and considering the
high density of 400-KOH-Ti3C2 (>3 g cm−3), the value for the
volumetric energy density could be even much higher than the
highest carbon based supercapacitors to date (19.5 W h L−1).[8]
This improvement in the performance was attributed to the
large space between Ti3C2 layers (the interlayer voids increased
from 2.0 to 7.7 Å), and lower terminal group concentration on
the MXene layers, which lead to more active sites (Ti atoms)
exposed to the electrolyte and more redox reactions. The new
strategy presented here is applicable to other MXenes materials
and make them promising pseudocapacitance electrode mate-
rials in real applications.
4. Experimental Section
Synthesis of Ti3C2Tx (T = F/OH) MXene: Ti3C2Tx were synthesized
as described in the previous report.[16] First, the Ti3AlC2 powders were
immersed slowly in a high density polyethylene beaker containing an
aqueous concentrated HF (30%) at room temperature (RT). Then, the
suspension was stirred at a speed of 700 rpm for 4 h at RT. Afterward,
the concentrated HF solution was decanted and the solids were filtered.
Fresh deionized (DI) water was then added to wash the obtained powder
several times until the pH value of liquid was higher than 4. Finally, the
washed powders were vacuum filtered to facilitate drying at RT.
Ion Intercalation and Surface Group Modification: The Ti3C2Tx flakes
were dispersed in 1.8 mol L−1 aqueous KOH solution (1 g MXene per
20 mL of aqueous KOH). The mixture was then stirred for 4 h at 700 rpm.
After that, the mixture was decanted, filtered. Fresh DI water was
added to wash the powders, and filtered to facilitate drying again. The
as-prepared Ti3C2Tx (T = F/OH) and KOH-Ti3C2 were then calcined at
673 K in Ar atmosphere, named as 400-Ti3C2Tx and 400-KOH-Ti3C2.
Other bases with different cation radius (NH4OH, LiOH, NaOH) were
also selected as the reagent for ion intercalation.
Characterization: The morphologies and structures of MXene
sheets were examined by SEM (Hitachi S-4800) and high-resolution
transmission electron microscopy (HRTEM, JEOL, JEM-2100).
Powder X-ray diffraction data were recorded using a Rigaku D/Max-
2000 diffractometer with graphite monochromatized Cu Kα radiation
(λ = 0.15406 nm) at 40 kV, 100 mA. Chemical compositions and
oxidation state of the samples were further analyzed using high-
resolution XPS with monochromated Al Kα radiation (hν = 1486.6 eV),
Binding energies were referenced to the C 1s peak of (CC, CH)
bond, which was set at 284.8 eV. The peak fitting was carried out using
commercially available software, CasaXPS. Ar adsorption–desorption
isotherms were measured by using a Micromeritics ASAP2020 device
at 77 K. Before the measurement, the sample was degassed at 473 K
for 10 h pretreatment. TG-MS was studied using a Netzsch Libra TG209
F1 thermogravimetric analyser coupled to a Netzsch Aëolos QMS 403C
quadrupole mass spectrometer from 298 to 873 K at a heating rate
of 5 K min−1 in Ar. FTIR spectroscopy experiments were performed
using a Thermo-Scientific Nicolet FTIR Model 8700 (in the range
4000–400 cm−1) equipped with a DTGS detector and a KBr beam splitter.
Before conducting FTIR experiments, the samples were treated under
473 K to remove the adsorbed water.
Adv. Energy Mater. 2017, 7, 1602725 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Electrochemical Characterization: To fabricate electrodes, 50 mg active
Full paper
material (Ti3C2Tx, 400-Ti3C2Tx (T = F/OH), KOH-Ti3C2, 400-KOH-Ti3C2)
powders were mixed in 5 mL N-methyl-2-pyrrolidone (NMP) to form a
10 mg mL−1 of homogenous slurry. Polyvinylidene fluoride (PVDF) of
5 wt% was added as binder and acetylene black was added to create
a conductive network in between the MXene sheets The mass ratio of
MXene and PVDF and acetylene black was 90:5:5. A 100 µL of slurry was
coated onto a porous carbon foam (area of 1 cm × 2 cm and 1.2 mm
thick, as current collector shown in Figure S1a, Supporting Information)
with the mass loading of ≈0.5 mg cm−1 and then dried under vacuum at
100 °C for 10 h to remove NMP. The measured specific capacitance of
the pristine carbon foam with a density of 1.1 mg cm−2 is about 30 F g−1.
The electrochemical measurements were performed in three-electrode
Swagelok cells, in which MXene served as the working electrode,
platinum was used as the counter electrode, and Ag/AgCl in 3 m KCl
was the reference electrode. 1 m H2SO4, 1 m Li2SO4, 1 m Na2SO4, and 1 m
K2SO4 were selected as electrolytes to investigate the influence of cation
radius in electrolyte on supercapacitor performance for MXene sheets.
CV tests and galvanostatic charge–discharge (CC) tests were performed
in the range of −0.2 to 0.4 V using an electrochemical analyzer, CHI
660E, under ambient conditions. Electric impedance spectroscopy (EIS)
was performed with an amplitude of 10 mV, from 10 mHz to 100 kHz.
For the ex situ XPS measurement, MXene served as the working
electrode, platinum was used as the counter electrode, Ag/AgCl in 3 m
KCl was the reference electrode, and 1 m H2SO4 as the electrolyte. Before
conducting the XPS test, the cell was subjected to 20 CV cycles at a scan
rate of 10 mV s−1 in the potential range of −0.2 to 0.4 V, after which at
the scan rate of 1 mV s−1 was performed. When the sweeping potential
was at 0.4 and −0.2 V, the CV test was stopped and then XPS data of
the working electrode were collected. TiO and anatase TiO2 were chosen
as reference to estimate the Ti oxidation state in Ti3C2Tx and 400-KOH-
Ti3C2 at applied potentials (i.e., −0.2 and 0.4 V). The dominant Ti 2p3/2
components centered at 458.8 and 454.8 eV are associated with TiO2
and TiO.
A symmetric electrochemical cell, which had a two-electrode
configuration, was fabricated in 1 m H2SO4. The electrodes of 400-KOH-
Ti3C2 MXenes were prepared in a similar way as described above with
an area of 2 cm × 2 cm and mass loading of ≈0.5 mg cm−1 but the
current collector was replaced by carbon cloth (Figure S2b,c, Supporting
Information). In order to perform life cycle test, the mixed solution of
1 m H2SO4 and 1 m Li2SO4 solution was employed as the electrolyte and
the two electrodes were separated by a thin polymer separator (Celgard
3501).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors gratefully acknowledge the financial supports from
the National Basic Research Program and the National Natural
Science Foundation of China (Nos. 21527803, 21471009, 21321001,
2013CB933402, 11275012, and 2016YFA0301004).
Received: December 7, 2016
Revised: January 7, 2017
Published online: March 6, 2017
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