Electrochimica Acta 337 (2020) 135803

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A safe etching route to synthesize highly crystalline Nb2CTx MXene for

high performance asymmetric supercapacitor applications
Junpeng Xiao , Jing Wen , Jiabao Zhao , Xinzhi Ma , Hong Gao *, Xitian Zhang
Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin
NormalUniversity, Harbin, 150025, PR China

a r t i c l e i n f o a b s t r a c t

Article history: We present a novel strategy to prepare Nb2CTx by etching Nb2AlC powders with a mixed solution of
Received 21 September 2019 lithium fluoride and hydrochloric acid. The Nb2CTx exhibits a layered structure with excellent crystalline
Received in revised form degree and structural order. Meanwhile, the electrochemical performance of Nb2CTx in aqueous elec-
17 January 2020
trolyte was examined for the first time. The Nb2CTx shows good electrochemical capacitance perfor-
Accepted 27 January 2020
Available online 30 January 2020
mance, and the addition of carbon nanotubes (CNT) as a conductive agent can significantly improve the
rate performance of the electrode. This may provide an idea to improve the performance for the M2C-
type MXenes electrodes with lower conductivity than Ti3C2Tx. The asymmetric supercapacitor was
Keywords:
MXenes
assembled by using Nb2CTx/CNT as negative electrode and activated carbon as positive electrode, which
Nb2CTx can deliver a high energy density of 154.1 mWh/cm2 and a maximum power density of 74843.1 mW/cm2
Asymmetric supercapacitor under the high mass loading. The power density is higher than most of the reported MXene-based
Aqueous electrolyte supercapacitors.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction for an early transition metal (such as Ti, V, Nb, etc.), A corresponds
to IIIA or IVA group elements (such as Al, Si), and X represents C
With the depletion of fossil energy and the aggravation of and/or N [6e8]. The synthesized 2D MXenes always need func-
environmental pollution, the development and application of tional groups, such as eOH, eO, eF, etc, on the surfaces to stabilize
environment-friendly clean energy has become the top priority of the layered configuration [2,9], which can transform the chemical
human sustainable development. Electrochemical capacitor as an formula of MAX from Mnþ1AXn (n ¼ 1,2,3) to Mnþ1XnTx (MXenes),
ideal energy storage device has attracted extensive attention due to where T represents the surface functional groups and x stands for
its remarkable advantages such as long cycle life, high power the number of termination groups [2,9]. So far, a variety of MXenes
density and high stability under high rate charge and discharge. phases have been reported, including Ti3C2Tx [1,2,10], Ti2CTx [11],
However, the current commercial supercapacitors mainly use low- V2CTx [12], Nb2CTx [12], Nb4C3Tx [4], Mo2C [13] etc. Among these
capacitance carbon materials as the negative electrode, which materials, Ti3C2Tx is the most widely studied system in this family
greatly affects the energy density and capacitance of the device, so due to its superior intercalation pseudocapacitive behaviors and
the development of high-performance negative materials has electronic conductivity [10,14,15]. Especially in aqueous electro-
become a key factor. In 2011, Naguib et al. firstly reported that two- lytes, it has been reported that the capacitance of pure Ti3C2Tx can
dimensional (2D) Ti3C2Tx can be obtained by etching Ti3AlC2 reach up to over 400 F/g [16], but its large molecular mass with
powder in HF solution [1], leading to the discovery of a large family multiple atomic layers in each formula unit (f.u.) limits its specific
of 2D materials usually labelled as MXenes [2e5]. Most of the capacity.
samples can be derived from the A-containing MAX phases by For Nb2CTx, it is one of the materials with the few atomic layers
removing the A-layers through different etchants, where M stands (3 layers) configuration in MXenes, and it is also one of the most
promising electrode materials for lithium-ion batteries [17] In
addition, Nb2CTx lithium ion capacitors have also been reported.
* Corresponding author. The electrochemical behavior of delaminated Nb2CTx/CNT com-
E-mail addresses: 3192867003@qq.com (J. Xiao), wenj674@126.com (J. Wen), posite electrodes is superior to their layered Nb2CTx [18,19]. How-
1807669000@qq.com (J. Zhao), maxz0224@126.com (X. Ma), gaohong65cn@126. ever, the supercapacitor properties of Nb2CTx electrodes in aqueous
com (H. Gao), xtzhangzhang@hotmail.com (X. Zhang).

https://doi.org/10.1016/j.electacta.2020.135803
0013-4686/© 2020 Elsevier Ltd. All rights reserved.
2 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803

electrolytes have not been reported. The electronic conductivity of structure. Therefore, we increase the temperature and provide
Nb2CTx film (24 S/cm) [20] is two orders of magnitude smaller than pressure to meet its etching conditions, and extend the reaction
that of Ti3C2Tx film (~103 S/cm) [21,22]. It may be one of the reasons time to achieve sufficient etching. The Nb2CTx were synthesized by
to hinder its application in aqueous supercapacitors. It can be found etching Nb2AlC powders (＜38 mm particle size) in a mixed solu-
that the atomic layer number may exert significant influence on its tion of lithium fluoride (1.6 g) and hydrochloric acid (20 ml) for
electrochemical properties based on the reported results. For 90 h at 60  C (React in closed conditions). The resulting mixture was
example, the capacitance of V2CTx film electrode is twice as large as then centrifuged at 8000 rpm for 5 min, and the supernatant was
that of one of reported Ti3C2Tx film (prepared by vacuum filtration immediately poured out. The obtained sediment was centrifuged
and tested under the similar conditions)[23,24], but the rate three times at 8000 rpm with 1 M HCl and 1 M LiCl aqueous so-
retention of the Ti3C2Tx and V2CTx film electrodes are 58% and 35%, lution, respectively. Then the mixture was centrifuged several times
respectively. The difference in capacitance and rate performance at 8000 rpm with deionized water, and the wet sediment was
may be due to the differences in atomic layer number in each f.u. collected. Finally, the wet sediment was dried for 12 h at 60  C in
and conductivity (385 S/cm for V2CTx film [25], which is about one vacuum oven to obtain the Nb2CTx powders.
tenth of the Ti3C2Tx film [22]). Furthermore, it has been reported
that the electronic conductivity of MXenes can be strongly 2.2. Fabrication of Nb2CTx/CNT and Nb2CTx electrodes
dependent on the number of atomic layer in each f.u. with the
consistent functional groups [26]. These results show the possi- The Nb2CTx/CNT electrodes were prepared with Nb2CTx,
bility that the rate performance of Nb2CTx in aqueous electrolyte MWCNT and poly (vinylidene fluoride) (PVDF) binder in a weight
may be affected by its atomic layer number in terms of electronic ratio of 8:1:1, and the Nb2CTx electrode was prepared with Nb2CTx
conductivity. It needs a high-quality sample to realize the electro- and PVDF binder in a weight ratio of 9:1. For comparison, the
chemical test of Nb2CTx in aqueous electrolyte, which poses a Nb2CTx/acetylene black (AB) electrodes has also been prepared
challenge to the synthesis method of high crystalline Nb2CTx. At with Nb2CTx, AB and PVDF binder in a weight ratio of 8:1:1. A small
present, most of the layered Nb2CTx were successfully prepared by amount of N-methyl-2-pyrrolidone (NMP) solvent was added to
treating Nb2AlC in 50% aqueous HF solution as reported by Naguib the mixture with vigorous stirring and ultrasonic to form homo-
et al. [12]. The delaminated Nb2CTx can be further obtained by geneous slurry. The slurry was then coated onto Carbon paper
adding intercalating agents such as tetrabutylammonium hydrox- (surface area 1 cm2) and dried in a vacuum oven at 60  C overnight
ide or isopropylamine [19,27]. It is well known that the use of HF as working electrodes.
solution poses a high risk to the experimental process, and the high
concentration of HF solution will seriously damage the crystal 2.3. Characterization
structure of the product, resulting in a decrease in crystallinity of
the sample [2]. In contrast, the delaminated Ti3C2Tx can be pre- X-ray diffraction (XRD, D/max 2600, Rigaku, Japan) was used to
pared by etching Ti3AlC2 using a mild mixed solution of hydro- characterize crystal structure of the Nb2CTx powders (Cu Ka radi-
chloric acid and lithium fluoride [2], which is a safe and efficient ation, l ¼ 1.5418 Å). Scanning electron microscopy (SEM, SU70,
method, but not used in the preparation of Nb2CTx. This may be due Hitachi, Japan) equipped with an energy dispersive X-ray spec-
to the high bond energy of NbeAl in Nb2AlC in contrast to the lower troscopy (EDS) were used to characterize the morphology and
TieAl bond in Ti3AlC2 [28]. The mild solution of hydrochloric acid element composition the Nb2CTx powders. The atomic structure of
and lithium fluoride is not effective for the rapid etching of Nb2AlC the sample was characterized by using the transmission electron
under the similar condition. microscopy (TEM, FEI, Tecnai TF20). Chemical compositions of the
In this paper, we successfully prepare Nb2CTx by using the samples were further analyzed by employing the X-ray photo-
etchant of lithium fluoride and hydrochloric acid. The product ob- electron spectroscopy (XPS, PHI 5700 ESCA System, American).
tained by this method exhibits a better crystal structure. Mean- Specific surface area was calculated by using the Brunauer-
while, the electrochemical performance of Nb2CTx supercapacitor Emmett-Teller (BET) equation.
in aqueous electrolyte was improved by adding the multi-walled
carbon nanotubes (MWCNT) as a conductive agent, which ex- 2.4. Electrochemical measurement
hibits good capacitance properties. This may provide an idea for
other MXenes electrodes with relatively low electronic conductiv- Electrochemical testing was performed using an electro-
ity compared to Ti3C2Tx. Based on the sample, Nb2CTx/CNT//acti- chemical workstation (VMP3, France) with a standard three elec-
vated carbon (AC) asymmetric supercapacitors (ASC) was trode electrochemical configuration. 1 M H2SO4 solution was
assembled. The cell shows the good area capacitance, area power chosen as electrolyte, Ag/AgCl and carbon were used as reference
density and energy density and can be significantly improved by and counter electrode, respectively. The electrochemical perfor-
regulating the electrode load. These results provide a route to mance of the as-prepared electrodes was studied by means of the
prepare the high-crystalline Nb2CTx as a high-performance asym- cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD)
metric supercapacitor electrode material. techniques with the potential window from 0.35 V to þ0.2 V.
Moreover, the electrochemical impedance spectroscopy (EIS)
2. Experimental section measurements were performed by applying an alternating-current
voltage with 10 mV amplitude in a frequency range from 10 mHz to
2.1. Synthesis of the Nb2CTx MXene 200 kHz.

Due to the difference in the number of valence electrons of Ti 2.5. Assembling of the asymmetric supercapacitor
and Nb, the etching of Nb2AlC under the similar condition for
preparing Ti3C2Tx (using a mild mixed solution of hydrochloric acid The device was assembled by using the Nb2CTx/CNT as the
and lithium fluoride at 38  C for 48 h [2]) is almost ineffective. It has negative electrode, activated carbon (AC) as the positive electrode.
been proven that the bond energy of NbeAl is stronger than that of 1 M H2SO4 was chosen as the electrolyte and filter paper as the
Ti-Al [28], so some experimental conditions need to be increased to separator. The CR2032 battery button was employed to package the
achieve its effective etching but without destroying the host Nb2CTx/CNT//AC ASCs. In the preparation process, the load of the
 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803 3

positive and negative electrodes should be properly controlled to microscopy (HRTEM) measurements were performed. Due to the
ensure that utilizations of the positive and negative electrodes are large size of Nb2CTx with layered structure, the samples were tested
sufficient (the mass ratio of Nb2CTx to AC is about 1:1.16). The tests by HRTEM after ultrasonic dispersion. The HRTEM image (Fig. 1c)
were performed by using a two-electrode test system in the elec- and selected area electron diffraction (SAED) pattern (inset in
trochemical workstation (VMP3, France). Fig. 1c) taken from the sample along the (0001) plane displays a
clear atomic structure and a typical six-fold symmetric diffraction
pattern, indicating the good crystallinity in the basal planes of the
3. Results and discussion
sample. In Fig. 1c, the angle of the lattice fringes in different di-
rections is 60 , and the distance of lattice fringe in ab-plane is
Two X-ray diffraction (XRD) results for Nb2CTx and Nb2AlC are
approximately 0.27 nm, which is consistent with the interplanar
shown in Fig. 1a. Comparing the XRD pattern of the Nb2CTx powder
spacing calculated from the XRD data (2q ¼ 33.4 ). The lateral view
to its precursor, it is clear that the strongest diffraction peak at
can be observed from the curled edges as shown in Fig. 1d. The
2q ¼ 38.8 for Nb2AlC disappeared after treatment with the mixed
multilayer structures of Nb2CTx can be found and the thickness of
solution of lithium fluoride and hydrochloric. More importantly,
the interlayer space is about 1.20 nm, which is consistent with the
the (002) peak are shifted to lower angles compared with their
XRD measured results (Fig. 1a). Surface chemical analysis of the
location of pristine Nb2AlC. The phenomenon can be attributed to
Nb2CTx obtained from XPS shows three different peaks corre-
the expansion of the interlayer space along the c-axis as the Al is
sponding to Nb 3d, O 1s and C 1s, respectively. (Fig. 2a). In the C
replaced by functional groups. This is similar to the XRD patterns of
1s spectrum, four peaks of Nb2CTx can be found that correspond to
other MXenes [11]. For comparison, two XRD spectra for the
C]O (288.6 eV), CeO (286.4 eV), CeC (284.8 eV), and CeNb
different samples synthesized through HCl/LiF (Nb2CTx) and HF
(282.2 eV) bands (Fig. 2b), respectively, indicating that the pres-
(Nb2CTx-HF) etching methods have been given in Fig. S1 [29]. From
ence of CeO and CeC in the sample [12,30e33]. In the O 1s spec-
the sharp profile of the 002 peak obtained for the Nb2CTx, the full
trum of Nb2CTx (Fig. 2c), O 1s due to Nb2O5 has a peak at 530.1 eV,
width at half maximum (FWHM) of the 002 peak is significantly
and two peaks at 532.3 eV and 531.0 eV belong to Nb2C(OH)x and
narrower than that of Nb2CTx-HF. With the similar morphology, the
Nb2COx, respectively, which correspond to the existence of eHO
Nb2CTx has a larger c-lattice parameter of 24.2 Å based on its (002)
and eO surface termination on the Nb2CTx [32e34]. In the Nb 3d
peak at 7.3 [12,19,27]. Scanning electron microscopy (SEM) anal-
spectrum (Fig. 2d), the peaks of CeNb bond is at 204.4 eV [33], and
ysis reveals that the prepared Nb2CTx is the typical morphology of
the peaks centered at 210.6 and 207.1 eV can be assigned to 3d3/2
stacked MXene, which shows a layered structure (Fig. 1b). Energy-
and 3d5/2 of Nb 3d (Nb5þ) in Nb2O5 [12,33]. These binding trends
dispersive X-ray spectroscopy images of Nb2AlC and Nb2CTx also
are consistent with the reported results of Nb2CTx [12,30e34].
show that the signal peak of Al almost completely disappears after
The addition of conductive AB is the usually accepted step to test
etching, and the Al atom content only remains 0.25% (Fig. S2). In
the performance of electrode, so the Nb2CTx/AB and Nb2CTx elec-
order to gaining further insight into the morphology and their
trodes were first tested under different scan rate test, but the
microstructure, the high resolution transmission electron

Fig. 1. (a) XRD patterns of Nb2CTx and Nb2AlC. (b) SEM image of Nb2CTx. (c) The HRTEM image of Nb2CTx. Inset presents its SAED pattern. (d) TEM images of the Nb2CTx with
multiple f.u. layers.
4 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803

Fig. 2. XPS spectra for the Nb2CTx (a), and high-resolution XPS spectra of C 1s (b), O 1s (c) and Nb 3d (d).

results of Nb2CTx/AB did not exhibit significantly improvement on Table S1, we can find that the capacitance of Nb2CTx/CNT is com-
the electrochemical performance as shown in Fig. S3. It has been parable with the reported value obtained from the optimized
expected that the addition of CNTs with excellent conductivity can sample with the similar molecular mass due to its improved
be used as an excellent conductive agent to improve the electro- interfacial reaction kinetics and configuration as discussed below.
chemical properties of Nb2CTx electrodes. Therefore, the electro- When the scan rate increases, the specific capacitances of the two
chemical performance of pure Nb2CTx and Nb2CTx/CNT electrodes electrodes exhibit different decreasing trends. As the scan rate in-
were tested in the 1 M H2SO4 aqueous electrolyte, respectively, creases from 2 mV/s to 100 mV/s, the Nb2CTx electrode only retain
using a conventional three-electrode asymmetrical setup. The the initial capacitance of 7.0%, which is much lower than the 72.3%
shape of the CV curves at scan rate of 2 mV/s exhibit the nearly ideal capacitance retention of Nb2CTx/CNT electrode. Fig. 3d gives the
rectangular shapes, indicating that the two electrodes have highly measured capacities of Nb2CTx/CNT at different current densities. It
capacitive behavior and great charging/discharging response at low is obvious that the curves of specific capacitances versus current
scan rate (Fig. 3a). When the scan rate is increased to 100 mV/s, the densities for the Nb2CTx and Nb2CTx/CNT electrodes also give the
CV curves of the Nb2CTx electrode are no longer rectangular, but the consistent trend as exhibited in Fig. 3c. It is clear that the addition of
CV curve of the Nb2CTx/CNT electrode is only slightly deviated from MWCNTs can significantly improve the rate performance of the
the rectangle, indicating that the Nb2CTx/CNT electrode still has electrodes. The Nyquist plots as shown in Fig. 3e derived from
good capacitance storage capability at high scanning rate (Fig. 3b). electrochemical impedance spectroscopy (EIS) measurements also
This difference can also be observed in the CV curves of the two give the supporting evidence for the improved charge transport of
electrodes at other scan rates (Fig. S4). Specific capacitances for the Nb2CTx/CNT in contrast to Nb2CTx. A low-frequency line region and
two electrodes at different scanning rate have been shown in high-frequency arc region, accompanied with the intercept of the
Fig. 3c. The values of Nb2CTx and Nb2CTx/CNT electrodes at 2 mV/s curve on the real axis can be observed in the Nyquist plots as in the
are 186 F/g and 202 F/g, respectively. From the XPS spectra, it can be general case [35e38]. For the two electrodes, the intercept, corre-
found that there is Nb2O5 exists in Nb2C MXene. In order to eval- sponding to the equivalent series resistance (ESR), are almost the
uating the influence of Nb2O5, the CV comparison data of Nb2O5/ same (0.75 U and 0.61 U for Nb2CTx and Nb2CTx/CNT electrodes,
CNT and Nb2CTx/CNT in H2SO4 electrolyte has been provided in the respectively). The size of the semicircle in the high frequency re-
supplementary information (Fig. S5), showing that Nb2O5 has gion is usually related to the charge transfer resistance (Rct) [35,36].
almost no capacitive contribution within the potential window. The relationship of 1=Rct feEb =kT is usually employed to define the
For comparison, a table of the specific capacitance of the resistance during the charge transfer processes, where Eb corre-
Nb2CTx/CNT electrode with other MXenes has been listed in the sponds to the activation energy of interfacial reaction, k and T are
supplementary information (Table S1). From the data listed in the Boltzmann constant and temperature, respectively [39,40]. The
 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803 5

Fig. 3. Electrochemical test images of Nb2CTx and Nb2CTx/CNT electrodes. (a) and (b) CV profiles at scan rates of 2 and 100 mV/s, respectively. (c) Specific capacitance vs. scan rate
images. (d) Specific capacitance vs. current density images. (e) Nyquist plots. (f) Characteristic relaxation time plots.

Rct of Nb2CTx and Nb2CTx/CNT are 0.43 U and 1.88 U, respectively. It performance of Nb2CTx/CNT electrodes at different mass loads
can be deduced that the reaction activation energy of Nb2CTx/CNT (from 1.5 mg/cm2 to 4.6 mg/cm2). Fig. 4a shows the CV curve of the
is relatively low, indicating that the Nb2CTx/CNT electrode has su- Nb2CTx/CNT electrodes in different mass loading at 2 mV/s with the
perior charge transfer behavior than Nb2CTx. In consideration of the consistent ideal rectangular shapes, indicating the stable specific
inferior electronic conductivity of Nb2CTx compared with Ti3C2Tx, capacitance with the increasing mass loading. When the scan rate
the significant improvement of charge transfer process can be ex- reaches 100 mV/s, the CV curve is no longer a regular rectangle as
pected that are mainly derived from the improvement of electron the load increases (Fig. 4b). From 2 mV/s to 100 mV/s, the capaci-
transport ability due to the addition of MWCNT as a conductive tance retention of the electrodes with loads of 1.5 mg, 2.6 mg,
bridge between Nb2CTx (as in the case of LiFePO4 with the additive 3.6 mg, and 4.6 mg are 72.3%, 58.7%, 51%, and 44.4%, respectively
of conductive carbon [41]). A parameter of characteristic relaxation (Fig. 4c). The decrease trend is expectable due to the decreased
time (t0) can also be employed to estimate this process, which is diffusion ability of electrolyte ions in the interior region of elec-
defined as the inverse frequency (t0 ¼ 1/f) of the peak in the C00 -u/ trode with high mass loading at high scan rates. In consideration of
2p curve based on the formula ofC0’ðuÞ ¼ Z0ðuÞ =ujZðuÞj2 to the importance of areal capacitance in practical applications, Fig. 4d
describe how fast the electrode can be charged or discharged and e shows the scan rate and mass load dependence of the area
[42,43], where C’’ (u) is the imaginary part of the capacitance C (u) capacitance. Obviously, as the mass loading increases, the area
and Z’ (u) is the real part of the impedance Z (u). The t0 of two capacitance increases and the rate performance decreases. The
electrodes was calculated to be 58.1 s and 2.8 s for the Nb2CTx and electrodes with the mass loading of 3.6 mg exhibits a high area
Nb2CTx/CNT electrodes respectively as shown in Fig. 3f, indicating capacitance of 727 mF/cm2 at 2 mV/s, and maintains an initial
that the Nb2CTx/CNT electrode has better reaction kinetics than capacitance of more than 50% when the scan rate reaches 100 mV/s.
Nb2CTx electrode. In addition, the improvement of Nb2CTx/CNT can This achieves a good tradeoff of capacitance and rate.
also be ascribed to the modified configuration of Nb2CTx/CNT. The Similarly, the specific capacitances for the four electrodes are
addition of MWCNTs results in a large amount of gaps between the calculated to be all about 200 F/g according to the discharge time at
Nb2CTx blocks accompanied with more active sites that can be 1 A/g from the galvanostatic charge-discharge (GCD) curves
exposed to the electrolyte, and thus provides more channels for ion (Fig. S8). When the current density increases from 1 A/g to 20 A/g,
transport and improve the ion accessibility. The N2 adsorption- the capacitance retention decreases as the load increases, consis-
desorption isotherms of the Nb2CTx and Nb2CTx/CNT can fully tent with the above CV analysis. From the EIS results for the four
support the above prediction (Fig. S6a). Compared with Nb2CTx, the electrodes, it can be found that the ESR values are almost the same
pore volume and specific surface area of Nb2CTx/CNT increased by (Fig. S9). It indicates that the ESR is nearly independent of the
2.6 times and three times, respectively (Fig. S6b). Furthermore, the electrode mass. At the same time, the Fig. 4f clearly shows that the
cycle performance of the Nb2CTx/CNT electrode at a large current characteristic relaxation time (t0) increases with increasing mass
density of 5 A/g was tested. The capacitance retention is 80.3% after load.
5000 cycles (Fig. S7), confirming its capacitive cycling stability. For further evaluating the energy density and power density of
In order to further evaluate the effect of mass loading on elec- the ACSs, the device of Nb2CTx/CNT//AC ASCs was assembled as
trochemical performance, we measured the electrochemical described above. In Fig. 5a, the working potential of Nb2CTx/CNT is
6 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803

Fig. 4. Electrochemical test images of Nb2CTx/CNT electrodes with different mass loading. (a) and (b) CV curves at scan rate of 2 mV/s and 100 mV/s, respectively. (c) Specific
capacitance vs. scan rate images. (d) and (e) The scan rate and mass load dependence of the area capacitance. (f) Characteristic relaxation time plots.

measured from 0.35 to 0.2 V, while the AC operating potential is density can be increased to 74843.1 mW/cm2 (Fig. 5d). Compared to
located from 0.2 to 1.0 V, which allows the effective cell voltage of other ASCs previously reported, Nb2CTx/CNT//AC ASC has higher
up to 1.35 V. The CV curves of the ASC at different voltage windows energy density and higher power density [44e52] (Fig. 5e and f). In
at a scan rate of 20 mV/s shows that the stable working voltage can contrast with the MnO2 dominated with surface-
reach 1.5 V (Fig. 5b). When the voltage is increased above 1.5 V, the pseudocapacitance contribution and graphene with the electric
CV curve becomes distorted. The CV curves for the four ASCs with double layer capacitance contribution, it can be found that the high
different loads exhibit good rectangles (Fig. S10), indicating that the value may come from the bulk involved pseudocapacitance
ASCs have good rate capability. From 2 mV/s to 100 mV/s, the behavior of Nb2CTx. The interlayer spacing of two-dimensional
capacitance retention of the ASCs with loads of 2.6 mg, 5.0 mg, Nb2CTx can facilitate the rapid diffusion of hydrated ions [53],
7.1 mg, and 10.0 mg are 74.6%, 74.4%, 68.1%, and 61.5%, respectively which provides a kinetics similar to the electric double layer
(Fig. 5c). Such great capacitance retention rate may be ascribed to capacitor and the available active sites in the bulk, ensuring its
the improved electronic transport of Nb2CTx/CNT and the good higher capacity and rate performances. In addition, the CNT im-
electronic conductivity of AC. It is worth noting that the areal proves the electron transfer processes, which leads to the Nb2CTx/
capacitance of ASC-2.6 is 132.6 mF/cm2 (51 F/g) at 2 mV/s, and the CNT negative electrode having good capacitance retention at high
areal capacitance of ASC-10.0 reaches 462.0 mF/cm2 when the load current density and pass to the Nb2CTx/CNT//AC ASC with good
is increased to 10.0 mg (Fig. 5c), closing to the proportional growth. charge and discharge ability under high mass loading. Furthermore,
In addition, the GCD curves of the four ASCs with different loads Nb2CTx/CNT can hinder the occurrence of polarization under a large
show good charge and discharge behavior (Fig. S11). Based on the work potential, which makes Nb2CTx/CNT//AC ASC overall voltage
results of the specific capacitance and areal capacitance at different window larger. These results indicate that Nb2CTx/CNT electrode
current densities obtained from the discharge time (Fig. S12), it can can be expected to be a promising candidate for supercapacitor
be found that the capacitance retention rate decreases with applications. These results indicate that Nb2CTx/CNT electrode is
increasing load, consistent with the above CV analysis. As a repre- expected to be a promising candidate for asymmetric super-
sentative, the cycle performance of ASC-2.6 at a current density of 5 capacitor applications.
A/g was tested (Fig. S13). The capacitance retention is 73.3% after
2000 cycles. The energy and power density of the ASCs can be 4. Conclusions
obtained from the GCD curves at different current densities. It can
be observed that the energy density of ASC-2.6 is 16.5 Wh/kg at the In summary, we have reported a method for preparing Nb2CTx
current density of 0.5 A/g with the power density of 375.2 W/kg, by treating Nb2AlC with a mixed solution of lithium fluoride and
and the energy density still retains 10.1 Wh/kg at the current hydrochloric acid. This method reduces the risk during the exper-
density of 10 A/g. The power density can be increased to 7484.3 W/ iment. The Nb2CTx prepared by this method has excellent crystal-
kg (Fig. 5e). Connecting two ASCs in series can light up one LED (in line degree and structural order. Moreover, the electrochemical
the inset of Fig. S13). The ASC-10.0 exhibits an energy density of performance of Nb2CTx supercapacitor in aqueous electrolyte was
154.1 mWh/cm2 at a current density of 5 mA/cm2 with the power examined. Its electrochemical performance is significantly
density of 3750.4 mW/cm2, and the energy density still retains improved by adding MWCNT. This may provide an idea for other
50.8 mWh/cm2 at the current density of 100 mA/cm2. The power MXenes electrodes with lower electronic conductivity in contrast
 J. Xiao et al. / Electrochimica Acta 337 (2020) 135803 7

Fig. 5. (a) CV curves of Nb2CTx/CNT and AC electrodes at a scan rate of 20 mV/s (b) CV curves of the Nb2CTx/CNT//AC ASC at different voltages at a scan rate of 20 mV/s. (c) Areal
capacitance vs. scan rate for the ASCs with different mass loading. (d) Ragone plots of the ASCs with different mass loading. (e) and (f) Ragone plots of the ASC-2.6 and ASC-10.0. The
values reported for other ASCs are added for comparison. (ASCs corresponding to different loads are marked as ASC-2.6, ASC-5.0, ASC-7.1 and ASC-10.0, respectively.)

to Ti3C2Tx. By increasing the load of the electrode, the areal Jiabao Zhao: Formal analysis. Xinzhi Ma: Formal analysis, Soft-
capacitance of the electrode can be significantly increased under ware. Hong Gao: Conceptualization, Writing - review & editing.
the proportion of specific capacitance at the low scan rate. Xitian Zhang: Supervision.
Furthermore, an asymmetric supercapacitor, Nb2CTx/CNT//AC ASC
was assembled, and the areal capacitance, areal energy density and Acknowledgments
power density can be significantly increased by increasing the load
of the ASC. The maximum areal capacitance, areal energy density Project supported by the National Science Foundation of China
and areal power density of the large-load ASC-10.0 were 462.0 mF/ (No.51772070 and 51772069).
cm2, 154.1 mWh/cm2 and 74843.1 mW/cm2, respectively. Such an
ASC with large load provides a promising candidate of M2C-type Appendix A. Supplementary data
MXenes for application in high performance energy storage.
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2020.135803.
CRediT authorship contribution statement
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