Article

Cite This: ACS Nano 2019, 13, 3448−3456 www.acsnano.org

Carbon-Coated MoSe2/MXene Hybrid

Nanosheets for Superior Potassium Storage
Huawen Huang,† Jie Cui,‡ Guoxue Liu,† Ran Bi,† and Lei Zhang*,†
†
School of Chemistry & Chemical Engineering and ‡Analytical and Testing Centre, South China University of Technology,
Guangzhou 510640, PR China
*
S Supporting Information
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ABSTRACT: Potassium-ion batteries (PIBs) are attracting

intensive interest for large-scale applications due to the
high natural abundance of potassium sources. However, the
large radius of K+ makes it difficult for electrode materials
to accommodate the repeated K+ insertion and extraction.
Thus, developing high-performance electrode materials for
PIBs remains a great challenge. Herein, we present the
rational design and fabrication of hierarchical carbon-
coated MoSe 2 /MXene hybrid nanosheets (MoSe 2 /
MXene@C) as a superior anode material for PIBs.
Specifically, the highly conductive MXene substrate can
effectively relieve the aggregation of MoSe2 nanosheets and improve the electronic conductivity. Moreover, the carbon
layer enables us to reinforce the composite structure and further enhance the overall conductivity of the hybrid
nanosheets. Meanwhile, strong chemical interactions are found at the interface of MoSe2 nanosheets and MXene flakes,
contributing to promoting the charge-transfer kinetics and improving the structural durability. Consequently, as an anode
material for PIBs, the resulting MoSe2/MXene@C achieves a high reversible capacity of 355 mA h g−1 at 200 mA g−1 after
100 cycles and an outstanding rate performance with 183 mA h g−1 at 10.0 A g−1. The presented design strategy holds
great promise for developing more-efficient electrode materials for PIBs.
KEYWORDS: molybdenum diselenide, MXene, two-dimensional nanosheets, potassium-ion batteries, chemical interaction

N owadays, with the continuing development of electric

vehicles and smart power grids, there is ever-
increasing demand for next-generation energy storage
devices with high energy density and long cyclic life.1−5
Potassium-ion batteries (PIBs), which possess a similar
principle to lithium/sodium-ion batteries, have attracted
tremendous attention in large-scale applications due to the
high nature abundance of potassium sources.6−9 Moreover,
compared with Na+/Na, K+/K has a lower standard redox
potential, which can be translated into higher energy
density.10,11 However, the large radius of K+ (1.38 Å) makes
it difficult for electrode materials to accommodate the repeated
K+ insertion and extraction. During the past few years,
insertion type materials (e.g., carbonaceous and Ti-based
materials)12−16 have attracted much attention for PIBs because
of their stable cycling performance. Nevertheless, they often
suffer from relatively low theoretical capacities (<280 mA h
g−1). Additionally, although conversion reaction type (e.g.,
V2O3 and MoS2)17,18 and alloying type (e.g., Sn, Sb, and
Bi)19−21 electrodes have higher theoretical capacities (1000−
2000 mA h g−1) for PIBs, they are usually confronted with
huge volume changes upon cycling processes, resulting in the
structure collapse of active materials and further leading to
rapid capacity fading.22 Therefore, designing high-performance
electrode materials with robust structure for K+ storage is still a
great challenge.
Layered transition-metal dichalcogenides (LTMDs), a type
of two-dimensional (2D) material, have attracted considerable
attention as promising electrode materials for PIBs based on
conversion reaction mechanism with capacities of ∼1000 mA h
g−1.23−27 In particular, molybdenum diselenide (MoSe2), with
a sandwich-like lamellar structure, has been widely investigated
due to the large interlayer spacing (6.46 Å) that can
significantly reduce the structural resistance for K+ insertion
and extraction.28−30 However, due to the high surface energy
of 2D nanostructure, MoSe2 nanosheets generally tend to
agglomerate, giving rise to rapid capacity fading when used as
electrode materials. Varied strategies have been proposed to
relieve this problem, among which structure engineering is
widely practiced.31,32 For example, Guo et al. designed a core/
shell nanostructured MoSe2 as an anode material for PIBs,
which showed significantly improved cycling stability.33 In
addition, except for the aforementioned problem, the low
intrinsic conductivity of MoSe2 poses another threat to rate
Received: December 18, 2018
Accepted: February 28, 2019
Published: February 28, 2019

© 2019 American Chemical Society 3448 DOI: 10.1021/acsnano.8b09548

ACS Nano 2019, 13, 3448−3456
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Figure 1. Schematic of the preparation of MoSe2/MXene@C.
performance, especially under high current densities. To
address this issue, a common approach is to couple MoSe2
with conductive materials, such as carbonaceous materials, to
effectively enhance the conductivity and stability of MoSe2-
based electrodes.34−38 For example, carbon-coated MoSe2
nanosheets, in which the MoSe2 were uniformly covered by
a conductive carbon layer, exhibited significant improvement
of the K+ storage performances.39 In this regard, simulta-
neously engineering the structure and composition of MoSe2-
based nanocomposites is supposed to comprehensively over-
come related problems, aiming to construct optimal material
design toward superior potassium storage properties. In
contrast, individual structure or composition optimization
strategy can only improve the cyclability of MoSe2-based
anode materials to a limited extent. Integrating both above-
mentioned strategies (that is, to regulate MoSe2 nanostructures
with assistance of other conductive substrate materials) is
expected to boost the resulting K+ storage performances.
MXene, a new graphene-like 2D material identified as
transition-metal carbide and carbonitrides, has been regarded
as a functionalized substrate material for electrochemical
energy storage because of its metallic conductivity and rich
surface functional groups.40−44 It is worth mentioning that the
surface chemical groups of MXene can act as a basis for the
nucleation and thereby anchoring other active materials.45,46
For instance, Qiu et al. reported MoS2 nanoplates on MXene
sheets stabilized by a carbon layer, which displayed excellent
electrochemical properties as an anode material for Li-ion
battery.47 The excellent properties could be attributed to the
highly conductive functionalized MXene substrate that could
effectively relieve the aggregation of MoS2 nanosheets and
enhance the conductivity of electrode material. Besides, other
active materials such as black phosphorus quantum dots and
TiO2 nanorods have also been successfully supported by
MXene as improved composite anode materials for Li-ion
batteries.48,49 Notwithstanding these advances, the rational
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design of MXene-based electrode materials for PIBs has rarely
been explored and is therefore deserving of study.
Herein, MoSe2 nanosheets were grown on highly conductive
MXene flakes via the hydrothermal method, then the as-
prepared MoSe2/MXene hybrid nanosheets were coated by a
polydopamine (PDA)-derived carbon layer (denoted as
MoSe2/MXene@C) to unlock the potassium storage capa-
bility. In particular, the MoSe2 nanosheets were anchored on
the MXene substrate vertically to form a hierarchical 2D
nanosheets structure, which could effectively prevent the self-
aggregation of MoSe2 nanosheets and improve the con-
ductivity of the hybrid material. Furthermore, the carbon
coating on the hybrid nanosheets was beneficial for reinforcing
the hierarchical 2D structure and further enhancing the
conductivity of the composite. Meanwhile, strong chemical
interactions were found at the interface of MoSe2 nanosheets
and MXene flakes, contributing to promoting the charge-
transfer kinetics and improving the structural durability. When
evaluated as an anode material for PIBs, the MoSe2/MXene@
C showed an ultrastable cycling performance with high
reversible capacity of 355 mA h g −1 at 200 mA g−1 after
100 cycles. Impressively, the composite material demonstrated
an outstanding rate performance with 183 mA h g−1 at 10.0 A
g−1, and the capacities can be restored well after switching to
quondam currents.
RESULTS AND DISCUSSION
The preparation procedures of MoSe2/MXene@C are
illustrated in Figure 1. First, MXene flakes are synthesized
and used as conductive substrate (see the Methods section and
Figure S1 for details). Then, using sodium molybdate as the
molybdenum source and Se powder as the selenium source,
MoSe2 nanosheets were vertically grown on the surface of
MXene flakes through hydrothermal reaction to obtain
MoSe2/MXene hybrid nanosheets. Afterward, the as-prepared
MoSe2/MXene was coated with polydopamine (MoSe2/
MXene@PDA) and then annealed in H2/Ar atmosphere at
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Figure 2. (a, b) FESEM images at different magnifications, (c) TEM image, (d) HRTEM image, (e) HAADF image, and (f) corresponding
mapping images for Se, Mo, C, and Ti elements of MoSe2/MXene@C.

Figure 3. (a) XRD pattern of MoSe2/MXene@C. (b) XPS survey spectrum and high-resolution spectra of (c) C 1s and (d) O 1s of MoSe2/
MXene@C.

600 °C to obtain MoSe2/MXene@C. Specifically, as shown in
the atomic model of MoSe2/MXene, MoSe2 nanosheets were
anchored on MXene flakes through strong covalent bonds,
significantly improving the stability of hybrid structure and
promoting the transfer kinetics of ions and electrons during
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charge and discharge processes. Moreover, the MoSe2/MXene
hybrid nanosheets were coated by a uniform carbon layer
shown in atomic model of MoSe2/MXene@C, which can
effectively reinforce the hierarchical 2D nanostructure and
further enhance the overall conductivity.
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Figure 4. (a) CV curves of MoSe2/MXene@C at a scan rate of 0.1 mV s−1. (b) Comparison of cycle performance of MoSe2/MXene@C,
MoSe2/MXene, MoSe2, and MXene at 200 mA g−1 along with corresponding Coulombic efficiency of MoSe2/MXene@C. (c) Comparison of
rate performance of MoSe2/MXene@C, MoSe2/MXene, MoSe2, and MXene at various current densities. (d) Long-term cycling discharge
capacities and Coulombic efficiencies of MoSe2/MXene@C at the current densities of 1.0, 2.0, and 5.0 A g−1.

The morphology of the as-prepared materials was
characterized by field-emission scanning electron microscopy
(FESEM) and transmission electron microscopy (TEM). The
FESEM image of MoSe2/MXene (Figure S2a) shows that the
MoSe2 nanosheets are vertically anchored on both sides of the
MXene flakes. Corresponding TEM image (Figure S2b) and
the high-resolution TEM (HRTEM) image (Figure S2c)
clearly indicate the hierarchical 2D nanosheets structure of
MoSe2/MXene. As shown in Figure 2a, after coated by a PDA-
derived carbon layer, the MoSe2/MXene@C has well-
preserved hierarchical 2D nanosheets structure similar to that
of MoSe2/MXene precursor. The enlarged view of the 2D
composite structure (Figure 2b) reveals that the MoSe2
nanosheets fully cover the MXene surface to form a three-
dimensional interconnected porous network. The successful
growth of the ultrathin MoSe2 nanosheets on the surface of
MXene is also confirmed in the TEM images (Figures 2c and
S3). The HRTEM image (Figure 2d) clearly reveals the lattice
fringes with an interlayer spacing about 0.72 nm, attributing to
an enlarged (002) lattice planes of MoSe2. Interestingly, it can
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be obviously observed that the MoSe2 nanosheets are covered
by a carbon layer with a thickness of about 2 nm. Additionally,
the high-angle annular dark field (HAADF) image (Figure 2e),
and the corresponding elemental mapping images (Figure 2f)
show an even distribution of the Se, Mo, C, and Ti elements in
the composite, which suggests that the MoSe2 nanosheets are
grown on the surface of MXene flakes uniformly and the
carbon layer evenly covers on MoSe2/MXene. Meanwhile, the
elemental contents of MoSe2/MXene@C were analyzed
through the energy-dispersive spectrometer in scanning
electron microscopy (SEM-EDS) (Figure S4). The contents
of MoSe2, MXene (Ti3C2), and coated carbon in the hybrid
nanosheets can be estimated to be 60.3, 6.2, and 31.2 wt %
based on SEM-EDS results and the stoichiometry of the
elements, respectively.
The crystal structure of MoSe2/MXene@C was further
analyzed using X-ray diffraction (XRD) pattern. As seen in
Figure 3a, all of the diffraction peaks could be well indexed to
hexagonal MoSe2 (JCPDS no. 29-0914; space group P63/
mmc, a = b = 3.287 Å, c = 12.925 Å). No impurity peak is
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detectable, implying the pure phase of as-prepared product.
The Raman spectrum of MoSe2/MXene@C (Figure S5)
confirms the formation of MoSe2 by the two characteristic
peaks of A1g and E12g located at 235.1 and 277.8 cm−1,
respectively. The A1g and E12g modes of MoSe2 were exhibited
as insets, where the A1g mode is preferred for edge-terminated
MoSe2 and the in-plane E12g mode is favored for terrace-
terminated MoSe2.30 Additionally, the two strong peaks at
1348.7 cm−1 (D peak) and 1593.6 cm−1 (G peak) of MoSe2/
MXene@C, respectively, correspond to the sp3 type and sp2
type of carbon atoms with an intensity ratio of 1.04 (ID/IG),
reflecting the existence of disordered carbon in the PDA-
derived coating layer. Furthermore, benefiting from the
hierarchical 2D nanostructure, the MoSe2/MXene@C exhibits
a larger Brunauer−Emmett−Teller (BET) specific surface area
of 44.7 m2 g−1 than that of MXene flakes (37.0 m2 g−1) (Figure
S6), contributing to facilitating the penetration of the
electrolyte and the diffusion of ions.38,47
X-ray photoelectron spectroscopy (XPS) spectra were
employed to get insight into the interfacial features between
the three components of MoSe2/MXene@C (Figure 3b−d).
In Figure 3b, the survey XPS spectrum of MoSe2/MXene@C
testifies the presence of O, Ti, Mo, Se, C, and N elements.34
The weight percentage of N in the composite is about 3.6 wt %
from the XPS analysis result. Additionally, the high-resolution
XPS spectra of Mo 3d, Se 3d, Ti 2p, and N 1s regions are given
in Figure S7.32,34,47,50 Specifically, the C 1s spectrum (Figure
3c) is fitted by four peaks at 284.6, 286.4, 288.2, and 282.8
eV.35,36,49 Compared with the C 1s spectrum of MoSe2/
MXene (Figure S8), it is evident to reach that the C−Ti bond
(282.8 eV) is originated from Ti3C2Tx MXene flakes. As
shown in Figure 3d, the O 1s XPS region can be fitted into four
peaks located at 530.2, 531.2, 532.0, and 533.3 eV.49,51 It is
noteworthy that the fitted peak at 532.0 eV could be attributed
to Ti−O−Mo bonds, indicating that covalent bonds are
formed at the interface between MoSe2 nanosheets and MXene
flakes, significantly increasing the interaction of the two
components.51−54 Importantly, the strong chemical interac-
tions are desired to enhance the structural durability and
improve electrochemical performances.35,47,52
We further investigated the potassium storage performances
of MoSe2/MXene@C as an anode material for PIBs. For
comparison, MoSe2/MXene without a carbon coating, pure
MoSe2 and MXene flakes were also prepared as control groups
(see the Methods section, Figure S1 MXene flakes, Figure S2
MoSe2/MXene, and Figure S9 MoSe2 for details). As depicted
in Figure 4a, the first three curves of the cyclic voltammogram
(CV) profiles of MoSe2/MXene@C were measured in the
potential range of 0.01−3.00 V at a scan rate of 0.1 mV s−1. In
the first cathodic sweep, 3 obvious reduction peaks at 0.86,
0.72, and 0.35 V can be clearly seen. The first one (0.86 V)
could be associated with the intercalation of K+ insertion into
the MoSe2 and the formation of KxMoSe2.34,39 The other two
peaks could be corresponded to the further reduction of
KxMoSe2 to metallic Mo and K5Se3 and the formation of the
solid electrolyte interphase (SEI) layer on the surface,
respectively.39 In addition, an obvious peak at 1.70 V is
observed in the subsequent anodic sweep, which can be
assigned to the oxidation of Mo to MoSe2.39 Notably, the
original three peaks disappear and two other new peaks at 1.60
and 1.15 V emerge in the following cathodic cycles, attributing
to the two stages of the reaction from MoSe2 to Mo and K5Se3
mentioned above. The shift of cathodic peak positions is
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related to the form of SEI film in the first cycle.35,37 The
cathodic and anodic peaks are similar in following scans.
Additionally, the charge and discharge processes of MoSe2/
MXene@C were further verified by galvanostatic profiles at
200 mA g−1 (Figure S10). The voltages of the discharge and
charge plateaus are consistent with the above results of the CV
profiles. Furthermore, the MoSe2/MXene@C electrode
delivers an initial discharge specific capacity of 641 mA h g−1
and a charge-specific capacity of 347 mA h g−1 with an initial
Coulombic efficiency (CE) of 54.2%. The low CE of the first
cycle can be mainly attributed to the irreversible reaction of
SEI film formation during the initial discharge process.35,37
The cycling performance of MoSe2/MXene@C at a current
density of 200 mA g−1 is shown in Figure 4b. As an anode
material for PIBs, the MoSe2/MXene@C retained a reversible
capacity of 355 mA h g−1 after 100 cycles with a high capacity
retention of 99.7% (compared with the second discharge
capacity, 356 mA h g−1), revealing a highly stable cycling
property. Expect for the first few cycles, stable CE approximate
99% were obtained in the following cycles as well. In the
meantime, the cycling performances of MoSe2/MXene, MoSe2,
and MXene at 200 mA g−1 had also been evaluated.
Concretely, MoSe2/MXene delivers a specific capacity of 104
mA h g−1, while pure MoSe2 only exhibits 65 mA h g−1 after
100 cycles. Pure MXene displays a stable but low capacity of
42 mA h g−1. Apparently, these results demonstrate that the
rational design of carbon coated MoSe2/MXene could
dramatically improve their potassium storage performances as
expected.
The rate performances of all as-prepared samples were
evaluated at varied current densities ranging from 0.1 to 10.0 A
g−1 (Figure 4c). As can be seen, the average specific capacities
of MoSe2/MXene@C are 350, 324, 294, 270, 246, 230, 212,
198, and 183 mA h g−1 at current densities of 0.1, 0.2, 0.5, 1.0,
2.0, 3.0, 5.0, 7.0, and 10.0 A g−1, respectively. All of these
results are much better than those of MoSe2/MXene, MoSe2,
and MXene, especially under high current densities. Notice-
ably, it could quickly resume a reversible capacity when the
current density changed back to small value (381 mA h g−1 at
0.1 A g−1). Compared with other TMDs anode materials for
PIBs, the as-prepared MoSe2/MXene@C shows a high rate
performance (Figure S11 and Table S1). In addition, high-rate
cycling performance was also measured on the MoSe2/
MXene@C anode material. Figure 4d shows the cycling
performances at high current density of 1.0, 2.0, and 5.0 A g−1.
Impressively, the three cycle curves are very steady with no
obvious fluctuation after the second cycle and retain capacities
of 317, 243, and 207 mA h g−1 at 1.0, 2.0, and 5.0 A g−1 after
300 cycles, respectively. The excellent rate performance of
MoSe2/MXene@C is mainly ascribed to the carbon coating
and the chemical interfacial interactions toward robust
structure and fast electron and ion transport.
The electrochemical properties of MoSe2/MXene@C are
better than those of the control groups. To get a deeper
understanding of the ultrastable cycling and rate performances,
the morphology of MoSe2/MXene@C after cycling has been
analyzed. As shown in Figure S12, the morphology of the as-
prepared MoSe2/MXene@C can be well maintained after
cycling test, illustrating the excellent structural stability of
MoSe2/MXene@C, which is beneficial to exhibit stable cycling
and rate performances. Furthermore, the electrochemical
impedance spectroscopy (EIS) results of MoSe2/MXene@C,
MoSe2/MXene, MoSe2, and MXene were measured and fitted
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Figure 5. (a) CV profiles of MoSe2/MXene@C at different scan rates. (b) The plots of log(i) vs log(υ) (peak current: i, scan rate: υ),
calculated from CV curves. (c) The shaded region shows the CV profile with the pseudocapacitive contribution at a scan rate of 1.2 mV s−1.
(d) Contribution ratio of pseudocapacitive at different scan rates.
with equivalent circuit to further explain the improved
electrochemical properties of MoSe2/MXene@C.29,35 As
shown in Figure S13 and Table S2, the MoSe2/MXene@C
exhibits smaller surface contact resistance and charge-transfer
resistance than those of MoSe2/MXene, MoSe2, and MXene,
indicating the higher transfer rate of potassium ions during the
continuous cycling. To further fully clarify the electrochemical
kinetics of the MoSe2/MXene@C electrode, the redox
pseudocapacitance-like contribution was analyzed. Figure 5a
exhibits the typical CVs at different scan rates ranging from 0.1
to 1.2 mV s−1. The relationship of the peak current (i) and the
scan rate (v) obeys a power law:55
i = avb (1)
where the b value can be calculated via the slope of the log(i)
versus log(v) plot, where the b value of 0.5 indicates diffusion-
controlled behavior and 1.0 represents pseudocapacitive effect.
As disclosed in Figure 5b, the b values of the anodic and
cathodic peaks are 0.93 and 0.86, respectively, manifesting that
the K+ storage kinetics of MoSe2/MXene@C is a combination
of diffusion-controlled and pseudocapacitive mechanism. The
contributions to the capacity can be further quantified by the
following equation:55
i = k1v + k 2v1/2 (2)
where k1v and k2v1/2 represent pseudocapacitive and diffusion-
controlled contribution, respectively (Figure 5c). With
increasing of the scan rate, the pseudocapacitive contribution
ratio becomes higher and the ratio value reaches 90.2% at a
scan rate of 1.2 mV s−1 (Figure 5d). The high pseudocapacitive
contribution of MoSe2/MXene@C is mainly due to its
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hierarchical 2D nanostructure, which effectively prevents the
self-aggregation of MoSe2 nanosheets, further creating a large
surface for the adsorption and desorption of K+ during the
discharge and charge processes.56−58 Additionally, the high
pseudocapacitive contribution is favorable for fast K+ storage
kinetics, which contributes to the excellent rate performance.
The excellent cycling stability and rate capability of the
MoSe2/MXene@C could be attributed to the rationally
designed hybrid nanostructure, constructing by the integrated
strategy of structure engineering and coupling with conductive
materials. Specifically, the hierarchical nanosheets structure
with ultrathin 2D nanosheets provides a short pathway for K+
diffusion and electron transport as well as large contact area
between the electrode and the electrolyte, leading to the
improved cycle stability and rate performance.35,54 It is worth
mentioning that the MoSe 2 nanosheets form a 3D
interconnected porous network on MXene flakes, effectively
preventing the self-aggregation of MoSe2 nanosheets and also
creating enough space to accommodate the volume change
during repeated K+ insertion and extraction processes.32,34
Furthermore, the carbon layer on the hybrid nanosheets can
reinforce the hybrid structure and improve the conductivity of
composite. Significantly, strong chemical interactions are found
in the interfaces of MoSe2 nanosheets and MXene flakes that
contribute to increasing the transfer kinetics of electrons and
improving the structural durability. All of these features
collectively ensure superior potassium storage properties of
MoSe2/MXene@C as a promising anode material for PIBs.35,52
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CONCLUSIONS
In summary, we have rationally designed and constructed a
hierarchical 2D nanostructure of carbon coated MoSe2/MXene
hybrid nanosheets. With the hierarchical 2D structure, carbon
coating, and the internal chemical interaction, the as-fabricated
MoSe2-based nanocomposite simultaneously integrates the
structural and compositional strategies for high-performance
electrode materials. When tested as an anode material for PIBs,
the resulting MoSe2/MXene@C exhibited high specific
capacity, excellent rate capability, and excellent cycling
stability. The present work provides a successful material
design strategy for the development of advanced electrode
materials for PIBs, which can be extended to other transition-
metal chalcogenide-based composites as superior anode
materials for potassium storage system.
METHODS
Preparation of Ti3C2Tx MXene Flakes. Ti3C2Tx sheets were
synthesized via etching of Ti3AlC2 powder.40 Typically, l.0 g of LiF
was dissolved in 20.0 mL of 9.0 M HCl solution. After stirring for
several minutes, 1.0 g of Ti3AlC2 powder was slowly added into the
mixture with magnetic stirring, which was kept stirring at 35 °C for 24
h. Afterward, a black suspension (pH ≈ 6) was obtained after
centrifugation and washing with DI water several times. The resulting
suspension was centrifuged at 3000 rpm for 1 h after ultrasonic
treatment for 1 h under flowing Ar. Finally, the black supernatant,
containing the suspension of the Ti3C2Tx (∼1.0 mg mL−1), was
collected for future use.
Preparation of MoSe2/MXene. A total of 79 mg of Se powder
was dissolved into 5 mL of N2H4·H2O (80%) solution by
continuously stirring for 1 h. Meantime, 121 mg of Na2MoO4·
2H2O was dissolved in 20 mL of DI water to obtain a transparent
solution. Then, 5 mL of prepared Ti3C2Tx MXene suspension was
added into the Na2MoO4 solution under stirring, and the mixed
solution was treated by ultrasonication for 1 h. Subsequently, the Se−
N2H4 solution was added to the mixed solution. The resultant
suspension was transferred into a 50 mL Teflon-lined stainless-steel
autoclave and heated at 200 °C for 12 h. After cooling to room
temperature, the product was collected by centrifugation and washed
with DI water and ethanol. Then, the black precipitate was dried at 60
°C in vacuum oven overnight and annealed at 600 °C in H2/Ar (8/
92, vol %) for 2 h. In comparison, pure MoSe2 was prepared in a
similar procedure without adding the Ti3C2Tx MXene flakes.
Preparation of MoSe2/MXene@C. A total of 45 mg of the
unannealed MoSe2/MXene powder was dispersed into 80 mL of Tris-
buffer solution (10 mM) by ultrasonic treatment for 1 h. Then, 25 mg
of dopamine hydrochloride was added rapidly into the mixture under
stirring at room temperature. The black precipitates were collected by
centrifugation and washed three times with DI water after stirring for
3 h. Subsequently, after drying at 60 °C in vacuum, the resulting
MoSe2/MXene@PDA was calcined under a H2/Ar (8/92, vol %)
atmosphere at 600 °C for 2 h to obtain MoSe2/MXene@C.
Material Characterizations. The microstructures were charac-
terized by field-emission scanning electron microscopy (SU8220, 10
kV) and transmission electron microscopy (JEOL JEM-2100F, 200
kV). XRD patterns were acquired via a Bruker D8 Advance
instrument with Cu Kα radiation (40 kV, 40 mA). XPS measurements
were conducted on X-ray microprobe of Thermo Escalab 250Xi with
monochromatic Al Kα radiation. Raman spectra were collected using
LabRAM Aramis with an excitation laser wavelength of λ = 532 nm.
The BET specific surface area of the samples were analyzed in a
Micrometrics 3 Flex N2 adsorption−desorption system.
Electrochemical Measurements. The electrochemical tests
were carried out in coin-cell configurations (CR2032) at room
temperature. The working electrodes consist of active materials (80
wt %), super P (10 wt %), and poly(vinylidene fluoride) (10 wt %).
Copper foil was employed as the current collector, and the electrodes
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were punched into discs with diameter of 8 mm. The mass loading of
active material on the electrode is about 1.0 mg cm−2. Fresh
potassium foils were used as counter and reference electrodes, and
Whatman glass microfiber filters (GF/F) were used as the separators.
The electrolyte was 1.0 M potassium bis(fluorosulfonyl)imide (KFSI)
in (EC/DEC, 1/1 vol %). The coin cells were assembled in an Ar-
filled glovebox (H2O < 0.1 ppm, O2 < 0.1 ppm). Galvanostatic
discharge−charge tests between 0.01 and 3.0 V were performed on
NEWARE battery testing system. CV curves were recorded using
GAMRY 1000E at different scanning rates. The electrochemical
impedance spectroscopy was collected at GAMRY 1000E in the
frequency range of 105 to 10−2 Hz.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.8b09548.
Additional SEM, TEM, SEM-EDS, nitrogen adsorp-
tion−desorption isotherms, XPS, XRD, Raman and
electrochemical data of the MoSe2/MXene@C, MoSe2/
MXene, MoSe2; and MXene; and a comparison of
MoSe2/MXene@C anode with recently reported TMDs
anodes for potassium-ion batteries (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: celeizhang@scut.edu.cn.
ORCID
Lei Zhang: 0000-0002-6385-5773
Author Contributions
H.H. carried out experiments, analyzed data, and wrote the
article; J.C. carried out TEM characterization; G.L. assisted in
the experiment and data analysis; R.B. and L.Z. planned the
project and participated in writing the article.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
Foundation of China (grant nos. 21606088 and 51621001),
the National Key Research and Development Program of
China (grant no. 2016YFA0202604), and the “Thousand
Talents Program”.
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3456 DOI: 10.1021/acsnano.8b09548

ACS Nano 2019, 13, 3448−3456