Research Article

www.acsami.org

Synthesis of MXene/Ag Composites for Extraordinary Long Cycle

Lifetime Lithium Storage at High Rates
Guodong Zou,† Zhiwei Zhang,† Jianxin Guo,† Baozhong Liu,†,‡ Qingrui Zhang,*,§ Carlos Fernandez,¶
and Qiuming Peng*,†
†
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, P.R. China
‡
School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, P.R. China
§
Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University,
Qinhuangdao 066004, P.R. China
¶
School of Pharmacy and Life Sciences, Robert Gordon University, Aberdeen AB107GJ, United Kingdom
*
S Supporting Information

ABSTRACT: A new MXene/Ag composite was synthesized by

direct reduction of a AgNO3 aqueous solution in the presence of
MXene (Ti3C2(OH)0.8F1.2). The as-received MXene/Ag composite
can be deemed as an excellent anode material for lithium-ion
batteries, exhibiting an extraordinary long cycle lifetime with a large
capacity at high charge−discharge rates. The results show that Ag
self-reduction in MXene solution is related to the existence of low-
valence Ti. Reversible capacities of 310 mAh·g−1 at 1 C (theoretical
value being ∼320 mAh·g−1), 260 mAh·g−1 at 10 C, and 150 mAh·
g−1 at 50 C were achieved. Remarkably, the composite withstands
more than 5000 cycles without capacity decay at 1−50 C. The
main reasons for the long cycle life with high capacity are relevant
to the reduced interface resistance and the occurrence of Ti(II) to
Ti(III) during the cycle process.
KEYWORDS: MXene, self-reduction, lithium batteries, composite

1. INTRODUCTION layer is 320 mAh·g−1,10 it decreases to 67 and 130 mAh·g−1 for

The performance of anode materials plays a crucial role in
lithium-ion batteries (LIBs);1 thus, extensive research efforts
have been devoted to exploring new anode materials with
better performance. Although Sn and Si possess very high
specific capacities, both of them experience large volume
changes during the cycle process, which causes powdering of
active materials and results in a sharp decrease in capacity.2,3
Therefore, developing new electrode materials with high
capacities at long cycles remains a challenge in LIBs.
Two-dimensional (2D) materials such as graphene,4
carbides,5 nitrides,6 oxides, and chalcogenides7 have recently
attracted broad interest because of their unique structural and
chemical properties, which make them promising electrode
materials for new-generation LIBs. Among these 2D materials,
the group of transition-metal carbides labeled as MXene
(Ti3C2(OHxF1−x)2), recently reported by Gogotsi and Barsoum
et. al.,8,9 are potential electrode materials for LIBs because of
their layered structure similar to that of graphite, providing
effective lithium storage space. However, the metallic Ti3AlC2
precursor is prone to form Ti 3 C 2 (OH) 2 and Ti 3 C 2 F 2
semiconductors when its surface is terminated with OH and
F groups, respectively. Therefore, though the theoretical
specific capacity of the metallic Ti3C2 conductor with one Li
Ti3C2(OH)2 and Ti3C2F2 semiconductors, respectively.11,12
Therefore, significant effort has been put into improving the
gravimetric capacity of the Ti3C2 conductor by modifying the
surface termination/state of MXene or by forming MXene-
based composites with other high lithium storage capacity
materials. For example, the capacity and cyclability of MXene
composites can be significantly improved by adding other
materials with large capacities and high conductivity such as
carbon additives,5 carbon-nanotube doping,13 and Sn4+ ion
intercalation.14 However, owing to the volume swelling and
weak conductivity, long cycle time and high-rate capacity in
MXene materials have not been achieved.
Notably, the exterior groups of MXene, which were prepared
by removing the Al layer from Ti3AlC2 in HF solution, not only
provide direct ion exchange sites15 but also act as an effective
reductant to some oxides such as Mn(VII), Cr(VI), and
Fe(III).16 This special reductive role offers a prerequisite to
tailor the chemical properties of MXene. Namely, some new
MXene-metal composites are expected to be synthesized in a
Received: July 5, 2016
Accepted: August 11, 2016
Published: August 12, 2016

© 2016 American Chemical Society 22280 DOI: 10.1021/acsami.6b08089

ACS Appl. Mater. Interfaces 2016, 8, 22280−22286
ACS Applied Materials & Interfaces
Figure 1. (a) Representative SEM image of the layered MXene/10Ag sample. (b) High-magnification image of a local area in panel a. (c) XRD
patterns of samples with different amounts of Ag. (d) Typical TEM image of the MXene/10Ag sample. The inset corresponds to the SAED along
the [1−10] direction. (e) High-resolution TEM image of a Ag particle. (f) Particle size distribution.
way in which the surfaces are covered by metal nanoparticles.
These materials have at least two-fold merits. The layered body
structure improves chemical properties of nanosized particles
by inhibiting aggregation and increasing electron transfer
efficiency. Conversely, the formation of nanoscale metallic
particles on the surface of MXene provides a great opportunity
to improve electrical conductivity of MXene, increasing
performance in both batteries and supercapacitors.
Herein, we report the synthesis of a new MXene/Ag
composite comprised of layered MXene templates and
nanosized Ag particles by direct reduction of a AgNO3 aqueous
solution in the presence of MXene. The layered MXene acts as
both a supporter and a reductant during the reaction process.
Attributed to the improved electronic conductivity and the
formation of Ti(III), this new MXene/Ag composite shows a
large capability at high charge−discharge rates and an
outstanding long cycle life when being used as an anode
material for LIBs.
2. EXPERIMENTAL SECTION
2.1. Preparation of MAX (Ti3AlC2). The powder mixtures of Ti
(99.5% purity, 325 mesh, Aladdin Reagent), C (99.5% purity, 2−4 μm,
Aladdin Reagent), and Al (99.95% purity, 200 mesh, Aladdin Reagent)
in a 1:1:1.8 molar ratio were sealed in a steel jar under an argon
protective atmosphere. Then, the mixtures were milled at 300 rpm for
4 h. After being milled, the mixtures were filled into a graphite die with
a diameter of 20.5 mm and sintered by a spark plasma sintering device
(SPS 3.20MK-IV, Sumitomo Coal Mining Co., Ltd., Japan) at 1350−
1400 °C under a pressure of 30 MPa. The soaking time was 10 min,
and the heating rate was 80 °C/min. After being sintered, the surfaces
of the samples were ground with SiC to remove the graphite layer.
Finally, the Ti3AlC2 bulk was milled at 400 rpm for 6 h to obtain the
Ti3AlC2 powder.
2.2. Preparation of MXene. MXene was prepared through a
conventional method. Briefly, MXene was synthesized by selectively
etching the aluminum layer out of the prepared Ti3AlC2 powder in
40% HF (Aladdin Reagent) for 10 h at room temperature. After HF
treatment, the solution was centrifuged and rinsed three times using
deionized water until the pH of the solution reached ∼5. Then, the
sample was dried in vacuum at 80 °C for 24 h.
22281
Research Article
2.3. Preparation of MXene/Ag Composites. MXene (100 mg)
was dispersed in 80 mL of deionized water and ultrasonically treated
for 30 min. After that, it was further stirred for another 10 min to
obtain a uniform suspension. In addition, 50 mg of AgNO3 (99.8 wt %,
Aladdin Reagent) was dissolved in 20 mL of deionized water. Taking
into account its low cost and easy storage, we used AgNO3 as our
silver salt instead of other silver salts. Then, the AgNO3 aqueous
solution was slowly injected into the uniform suspension. After
reacting for 10 min, the MXene/10Ag suspension was centrifuged and
rinsed three times using absolute ethyl alcohol. Finally, the MXene/
10Ag composite was dried in vacuum at 80 °C for 24 h. For
comparison, MXene/5Ag and MXene/15Ag composites were
synthesized under the same conditions as described above, except
the mass of AgNO3 was changed.
2.4. Cell Measurements. Cell measurements were performed
using coin-type 2016 cells with pure lithium metal as both the counter
electrode and reference electrode at room temperature. The working
electrodes, consisting of 80 wt % active materials (MXene or MXene/
Ag), 10 wt % acetylene black, and 10 wt % polyvinylidene fluoride
(PVDF), were prepared with the aid of N-methyl-2-pyrrolidinone
(NMP). The electrolyte was 1 M LiPF6 in the mixture of ethylene
carbonate (EC):dimethyl carbonate (DMC):ethylmethyl carbonate
(EMC) in a 1:1:1 volume ratio. The separator was a polypropylene
membrane (Celgard 2400). The cells were assembled in an argon-filled
glovebox with concentrations of H2O and O2 below 1.0 ppm. The
galvanostatic charge−discharge measurements were carried out using a
LAND-CT2001C test system at different current rates (1 C = 320
mAh·g−1) under the voltage between 0.01 and 3 V versus Li+/Li. The
cyclic voltammogram (CV) was obtained using an electrochemical
workstation (Biologic, VSP) at a scan rate of 0.2 mV/s from 0.01 to 3
V. Electrochemical impedance spectroscopy (EIS) was conducted on
an electrochemical workstation (Biologic, VSP) in the frequency
ranging from 100 to 0.01 kHz with an alternating current amplitude of
5 mV.
2.5. Analysis and Characterization. X-ray diffraction (XRD)
patterns were obtained with a powder diffractometer (Rigaku D/
MAX-2005/PC) using Cu Kα radiation (λ = 1.5406 Å) at a voltage of
40 kV and a current of 200 mA with a step scan of 0.02° per step and a
scanning speed of 2°/min.
A typical scanning electron microscope (SEM, Hitachi S4800,
Japan) was used to observe the microstructures of the samples.
Transmission electron microscopy (TEM) characterizations were
conducted on a JEOL JEM2010 transmission electron microscope
DOI: 10.1021/acsami.6b08089
ACS Appl. Mater. Interfaces 2016, 8, 22280−22286
ACS Applied Materials & Interfaces Research Article

equipped with a Gatan CCD camera working at an accelerating voltage account the low theoretical specific capacity of OH groups, we
of 200 kV. Elemental compositions were detected by an energy used the as-obtained MXene powder (Ti3C2(OH)0.8F1.2)17 for
dispersive X-ray (EDX) analyzer with an AMETEK/EDAX Genesis Ag reduction directly. The SEM image (Figure 1a) reveals that
attachment (EDAX Inc., Mahwah, NJ, United States) mounted on the
TEM. Nine random spots were performed to calculate the elemental
the layered structure of MXene remains. In addition, some
composition. All TEM samples were made by depositing a drop of particles were observed on the surfaces of MXene (Figure 1b).
diluted suspension in ethanol on a carbon film-coated copper grid. The From the XRD pattern (Figure 1c), there are four major
elemental contents (Ti and Ag) of the MXene/Ag composites were diffraction peaks which can be indexed to the (111), (200),
measured using inductively coupled plasma (ICP) (ICAP 6300 (220), and (311) planes of the face-centered-cubic Ag single
Thermo Scientific, United States). XPS analysis of given samples was crystal. The calculated lattice constant is 4.01 Å, which is close
performed with a spectrometer (ESCALAB-2, U.K.) equipped with a to the reported value.18 With increasing Ag concentration, the
Mg Kα X-ray source (1253.6 eV proton).
Ag peaks become sharper and the intensities increase,
3. RESULTS AND DISCUSSION indicating that the crystallinity of Ag is improved. In addition,
the (002) peak intensity of MXene at ∼9° becomes weak,
A typical exfoliation process of layered Ti3AlC2 powders was suggesting less order along c direction. The (002) peak position
performed by immersing them in 40% HF solution at room of MXene remains unchanged, implying that no Ag
intercalation occurs.
Table 1. Average Ag Particle Sizes Determined by Both XRD The TEM images (Figure 1d and e) reveal that the Ag
and TEMa particles mainly distribute on the surfaces of MXene/10Ag
elemental (containing ∼10 wt % Ag, Table 1). Ag nanoparticles are single
average Ag compositions crystalline, as evidenced by the sharp selected area electron
sizes (nm) (mg/L)
diffraction pattern (SAED) of a nanoparticle along the [1−10]
sample XRD TEM Ti Ag Ag concentration (wt %) zone axis. Examination of an individual nanoparticle with high-
MXene/5Ag 9 11 23.4 1.6 4.5 resolution TEM shows that it is a single crystal. The average
MXene/10Ag 28 34 13.2 2.0 10.2 particle size of Ag is ∼35.2 ± 5 nm (Figure 1f). Lattice figures
MXene/15Ag 157 180 8.5 2.1 15.6 with an interplanar spacing of d111 = 0.238 ± 0.02 nm are
a
In the XRD method, we used the Scherrer formula D = kλ/β cos θ, clearly visible. As the concentration of AgNO3 increases, both
where k = 0.9, λ = 0.154 nm, β = the broadening peak width at the half the size and amount of Ag particles increase correspondingly,
peak height in radians, and θ = Bragg angle to calculate the grain size. according to TEM observations as well as the average size
In the TEM method, the particle size was obtained by taking the calculated by the Scherrer formula (Figure S1 and Table 1).
average value of 20 particles). The elemental compositions were
confirmed by ICP testing.
They show the similar trends except that the particle size
calculated by the Scherrer formula is smaller than that
measured by TEM observation. The reason for the discrepancy
temperature.17 The average particle size of the starting Ti3AlC2 is that XRD patterns reflect an average bulk value, while TEM
is ∼3 μm. After being immersed in 40% HF solution at room results generally reflect a local area. With increasing Ag
temperature for 10 h, open arch-shaped edges at the ends of the concentration from 5 to 15%, the size of Ag particles increases
MXene layers resembling graphene were observed. Taking into from ∼10 nm to more than 100 nm, respectively.

Figure 2. (a) XPS profiles of the MXene and MXene/10Ag samples. (b) Ti 2p3/2 in the MXene. (c) Ti 2p3/2 in the MXene/10Ag. (d) Ag 3d3/2 in
the MXene/10Ag.

22282 DOI: 10.1021/acsami.6b08089

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Figure 3. Cyclic voltammetry curves of the MXene (a) and MXene/10Ag (b) samples at the initial 5 cycles. (c) Charge−discharge curves of the
MXene/10Ag sample at 1 C. (d) Comparative reversible delithiation capacity of the MXene and MXene/10Ag samples for 3000−5000 cycles.
Coulombic efficiency is plotted for the MXene/10Ag only. (e) Rate capabilities of the MXene and MXene/10Ag samples at different current rates
from 1 to 50 C. Coulombic efficiency is plotted for the MXene/10Ag sample with 1C only.

Table 2. Summary of the Electrochemical Performance of neously, the representative Ag 3d5/2 and Ag 3d3/2 peaks (Figure
Different MXene-Based Anode Materials at High Current 2d) are located at ∼367.8 and ∼373.8 eV with the slitting of the
Densities 3d doublet of ∼6.0 eV, suggesting the successful reduction for
Ag(0) formation. Additionally, considering the possible
current
density cycle presence of different Ag species, the Ag 3d peaks have been
component (C) number specific capacity (mAh·g−1) refs fitted using the software XPS peak fit after a Shirley background
delaminated 36 720 110 12 subtraction. Amazingly, nearly all silvers are in the Ag(0)
Ti3C2“paper” (metallic) state and the Ag+ and Ag2+ species are negligible,
In−Ti3C2 10 100 69 13 which further proves the strong reductive activity on the low-
exfoliated Ti2C 10 100 70 13 valence Ti(II) and Ti(III) species. Therefore, Ag self-reduction
Ti2C-based 10 1000 60 14 is ascribed to the activated low-valence Ti species.
negative
electrodes The electrochemical performance of the MXene and
Nb2CTx 10 150 110 23 MXene/10Ag composite as anode materials for LIBs was
electrodes investigated, and the typical CV curves at the initial 5 cycles are
V2CTx 10 150 125 23 shown in Figures 3a and b. Two broad irreversible reduction
electrodes peaks around 1.66 and 0.62 V were observed in the first
Ti3C2−CNF 1 300 320 24 lithiation process. It is mainly attributed to the formation of a
Ti3C2−CNF 100 2900 97 25 solid electrolyte interphase in combination with the inter-
MXene/10Ag 1 5000 310 this calation of Li+ between the sheets of MXene and MXene/Ag
work
MXene/10Ag 10 5000 260 this electrode materials.20 During the first delithiation process, two
work wide anodic peaks were detected at ∼1.96 and ∼2.44 V. In
MXene/10Ag 50 5000 150 this addition, a new peak at ∼0.37 V was detected in the MXene/
work 10Ag, which is attributed to the extraction of lithium ions from
the MXene/Ag electrodes.21−23 One possible reason for the
To elucidate the possible self-reduction mechanism, XPS presence of peak at ∼0.37 V was related to the formation of
investigation was conducted for MXene and MXene/10Ag transition-state Ti during the reduction processing,14 which
(Figure 2a). The distinct peak at ∼458.8 eV from primitive changes to some stable Ti compound after cycling. No
MXene samples is assigned to Ti(IV) 2p3/2 (Figure 2b). The significant peak shift in the subsequent cycles was found,
broad peak ranging from 453−457 eV suggests the possible indicating that the charge storage in both MXene and MXene/
presence of low-valence Ti species, i.e., Ti(II) (∼454.7 eV) and Ag electrode materials is the intercalation of Li+ rather than a
Ti(III) (∼455.8 eV)19 (Figure 2c). The self-reduction process conversion reaction.21
onto MXene/Ag (10 wt %) can lead to the initial trans- The representative galvanostatic charge−discharge potential
formation from Ti(III) to the terminated Ti(IV) species with curves of MXene/Ag composites and MXene at a current
the area fractions of 16.5 and 9.6%, respectively. Simulta- density of 1 C (320 mA·g−1) are shown in Figures 3c and S2a−
22283 DOI: 10.1021/acsami.6b08089
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Figure 4. (a) Nyquist plots of impedances for the MXene and MXene/10Ag samples after five cycles. The inset corresponds to the equivalent circuit
diagram. (b) Typical TEM image of the MXene/10Ag electrode after 2000 cycles. The inset shows the particle distribution (randomly measured 50
particles). High-resolution TEM images of the MXene/10Ag electrode after 5 cycles (c) and 2000 cycles (d) at 1 C. (e) Ti 2p3/2 in the MXene/10Ag
sample after 2000 cycles. (f) Ti 2d3/2 in the MXene/30Ag after 2000 cycles.

Table 3. Fitting EIS Results of Samples at Different States the grain size is smaller than the width of space-charge zones,23
resembling ionic charge carriers.19 Hence, the formation of Ag
error error
samples Rs (Ω) (%) Rct (Ω) (%) particles on the surface of MXene changes the electrical
MXene 2.773 0.8711 121.4 0.3626
properties of MXene substrate, accelerating Li+ ion diffusion
MXene/5Ag (after 5 cycles) 1.806 1.212 85.21 0.4914
along MXene layers.
MXene/10Ag (after 5 cycles) 1.237 1.067 59.28 1.128
Figure 3d shows the rate capability of the MXene and
MXene/15Ag (after 5 cycles) 1.534 0.6372 70.06 0.3461 MXene/10Ag samples at different current rates. Remarkably,
MXene/10Ag (after 100 cycles) 2.123 1.2321 92.61 0.3241 compared with MXene and other MXene/Ag composites
MXene/10Ag (after 800 cycles) 1.569 0.5126 71.61 0.3461 (Figure S3), the MXene/10Ag reveals better cyclic capacity
MXene/10Ag (after 1000 cycles) 1.413 0.8242 65.16 0.6124 retention at various current rates of 1−50 C. For the MXene, it
MXene/10Ag (after 2000 cycles) 1.353 0.6436 63.27 0.4388 exhibits a specific charge capacity of 220.0 mAh·g−1 at 1 C, and
MXene/10Ag (after 3000 cycles) 1.291 0.6197 60.45 0.7645 the capacity drops quickly to 131.5, 100.7, 86.6, and 47.4 mAh·
g−1 at 5, 10, 20, and 50 C, respectively. In the case of the
MXene/10Ag sample, a high capacity of 150.0 mAh·g−1
c. In the first discharge curves, the initial discharge capacities of
remains even at 50 C. Moreover, when the current density of
MXene and MXene/10Ag are ∼420 and ∼550 mAh·g−1,
charge rate returns to 1 C, the MXene/10Ag electrode recovers
respectively. However, their values decrease to ∼250 and ∼330
its previous reversible capacity value, implying its excellent rate
mAh·g−1 in the second cycle, respectively. In the subsequent
cycles, the charge−discharge capacity of MXene decreases reversibility. Figure 3e compares the cycling stability of the
continuously. Nevertheless, the overlap of the charge− MXene and MXene/10Ag electrodes. The MXene/10Ag shows
discharge curves after 800 cycles indicates good stability of a capacity of 310.0 mAh·g−1 at 1 C after 800 cycles, which is
the MXene/Ag electrodes. An obvious activation process that close to the theoretical capacity of the MXene/10Ag (320.0
was observed in the initial several hundred cycles was also mAh·g−1, the addition of Ag does not provide the capacity). A
observed in the MXene/Ag samples (Figure 3d). Further, the constant value of 260.0 mAh·g−1 at 10 C after 1000 cycles is
capacity below 1 V is about half of the reversible capacity for also observed. More attractively, the MXene/10Ag sample is
the MXene sample, which is consistent with both Ti3C2 and still able to provide a steady-state capacity of 150.0 mAh·g−1 at
Ti2C electrodes.11 On the other hand, the capacity fraction 50 C even after 5000 cycles. In contrast, the capacity of MXene
below 1 V is about two-thirds of that of the MXene/10Ag decreases with increasing cycles, and it finally reaches a steady
sample, which is similar to V2C-based MXene.22 Note that the value of 34 mAh·g−1 at 10 C after 500 cycles. The capacity of
narrow charge plateau at 0.37 V is more apparent at a low rate 150.0 mAh·g−1 at 50 C after 5000 cycles for the MXene/10Ag
of 0.3 C (Figure S2d). It is believed that the formation of is much higher than that of the broadly used graphite anode in
unstable transition-state Ti is easier to change to a stable Ti commercial LIBs. The latter loses more than 80% of its
compound at high-rate charge−discharge cycles. Thus, it is theoretical capacity to about 75 mAh·g−1 after ∼1000 cycles at
hardly detected at high rates. It is interesting that the voltage of 10 C.23 It is also much higher than those of other MXene
MXene/Ag dropped much more slowly than that of MXene in composites at high current rates reported so far (Table
region A of Figure 3c. The discharge process of region A is 2).12−14,23−25
mainly due to the homogeneous insertion of Li+ ions into the Figure 4a compares the Nyquist plots of the MXene and
interface of the matrix, which is associated with the size effects MXene/Ag electrodes after five cycles. The inset is an
that the potential profiles tend to become flatter initially when equivalent circuit model. The depressed semicircle in the
22284 DOI: 10.1021/acsami.6b08089
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ACS Applied Materials & Interfaces
high-to-medium frequency region and the inclined line in the
low-frequency range correspond to the charge transfer
resistance (Rct) and Warburg impedance (Ws) related to Li+
ion diffusion in the active materials, respectively.8,26 Apparently,
the fitting results (Table 3) indicate that the MXene/Ag
composites show lower values of charge transfer resistance than
that of the MXene. With suitable Ag concentration as well as
fine and homogeneous Ag nanoparticles, the smallest value of
59.28 Ω is achieved for the MXene/10Ag. Moreover, as the
cycle number increases, the particle size of Ag reduces (Figure
4b), and its distribution becomes more homogeneous (Figure
S4). Then, the interface fraction between MXene and Ag
increases, resulting in a decrease in both Rct and Ws (Figure S5
and Table 3). Thus, the electrolyte easily penetrates the
surfaces of MXene/10Ag layers and contributes to ion
diffusion, accelerating the intercalation of Li+ ions. For example,
the layer distance increases from 0.986 to 1.061−1.278 nm
when the cycles are increased to 2000 (Figures 4c and d and
S6). Therefore, as the cycles increase, the intercalation of Li+
occurs continuously, and the capacity is improved to close to its
theoretical value.
To further probe the presumable mechanism on activation
process-increased capacity during the cycle process, the amount
of variation of different valence Ti species was confirmed by
XPS. Interestingly, 2000 cycles of battery circulation can result
in an apparent fraction increase on Ti(III) (9.6 to 23.4%) and
weakened Ti(II) species (Figure 4e), indicating possible Ti
transformation from Ti(II) to Ti(III). It is well-known that
Ti(III) species can provide strong conductivity, which
significantly favors the excellent circulation property.27,28
Comparatively, the primitive MXene displays the negligible
Ti species variations after battery circulation, further proving
the important catalytic roles on Ag species (Figure S7a). In
addition, the high Ag loadings (30 wt %) can lead to a complete
oxidation of low-valence Ti(II) and Ti(III) species during the
self-reduction process, and no obvious Ti(III) species are
generated after 2000 cycles with the declining circulation
property (Figures 4f and S7b). It further demonstrates that the
efficient Ti (III) species originate from Ti(II) rather than
Ti(IV) reduction, revealing that the high loaded amount
fabrication is not always a smart choice.
4. CONCLUSIONS
In summary, this investigation offers a new method to fabricate
some novel MXene-metal composites with unique chemical
properties by means of direct reduction role of as-obtained
MXene materials. Taking Ag metal as an example, we prepared
a new MXene/Ag composite by directly reducing a AgNO3
aqueous solution with the addition of the as-obtained MXene
(Ti3C2(OH)0.8F1.2). The new MXene/10Ag composite is
deemed as a potential electrode material for Li-ion batteries
in terms of superior rate capability and excellent long-term
cyclability. It withstands more than 5000 cycles without
capacity decay at 1−50 C. We foresee an enormous potential
impact of this methodology in exploiting new physical and
chemical properties of different MXene-metal composites.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b08089.
22285
Research Article
SEM and TEM images, charge−discharge curves, cycling
performance graphs, EDS elemental distribution maps,
EIS curves, XRD patterns, and XPS profiles (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhangqr@ysu.edu.cn.
*E-mail: pengqiuming@gmail.com.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We greatly acknowledge financial support from NSFC (Grants
51422105, 51578476, and 51471065), The Science Foundation
for the Excellent Youth Scholars from Universities of Hebei
Province (Grant GCC2014058), NSF of Hebei Province
(Grant No. B2016203056) and the Natural Science Foundation
for Distinguished Young Scholars of Hebei Province of China
(Grant E2015203404), Heibei Province Youth Top-Notch
Talent Program. We also thank Dr. Yue Qi and Dr. Jianyu
Huang for their language check and beneficial discussion.
■
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22286 DOI: 10.1021/acsami.6b08089

ACS Appl. Mater. Interfaces 2016, 8, 22280−22286