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MoS2-Quantum-Dot-Interspersed Li4Ti5O12 Nanosheets

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with Enhanced Performance for Li- and Na-Ion Batteries
Guobao Xu, Liwen Yang,* Xiaolin Wei, Jianwen Ding, Jianxin Zhong, and Paul K. Chu*

materials such as Si,[5] transition metal

Rational nanoscale surface engineering of electroactive nanoarchitecture oxides,[6] transition metal dichalcoge-
is highly desirable, since it can both secure high surface-controlled energy nides,[2] and NASICON-type compounds,[7]
storage and sustain the structural integrity for long-time and high-rate production of suitable electrode materials
cycling. Herein, ultrasmall MoS2 quantum dots (QDs) are exploited as sur- with high-rate capability and ultrastability
face sensitizers to boost the electrochemical properties of Li4Ti5O12 (LTO). is still quite challenging. In addition, there
have been few investigations on the dual
The LTO/MoS2 composite is prepared by anchoring 2D LTO nanosheets
storage properties of lithium and sodium
with ultrasmall MoS2 QDs using a simple and effective assembly technique. based electrode materials.[8]
Impressively, such 0D/2D heterostructure composites possess enhanced Spinel Li4Ti5O12 (LTO) is a competi-
surface-controlled Li/Na storage behavior. This unprecedented Li/Na storage tive anode material for LIBs benefiting
process provides a LTO/MoS2 composite with outstanding Li/Na storage from stable charge/discharge platform
properties, such as high capacity and high-rate capability as well as long-term at 1.5 V, “zero-strain” in the lattice on
charging/discharging, and environmental
cycling stability. As anodes in Li-ion batteries, the materials have a stable benignity.[9,10] Recently, spinel LTO as an
specific capacity of 170 mAhg−1 after 20 cycles and are able to retain 94.1% anode material for NIBs has also been
of this capacity after 1000 cycles, i.e., 160 mAhg−1, at a high rate of reported.[11,12] Particularly, its relatively
10 C. Due to these impressice performance, the presented 0D/2D heterostruc- higher storage voltage versus Na/Na+ for
ture has great potential in high-performance LIBs and sodium-ion batteries. NIBs results in better cycle-life together
with improved safety compared with hard
carbon anode.[8] Various forms of LTO
nano/microstructures with improved LIB
1. Introduction performance have been prepared, for instance, nanoparticles,
nanowires, nanosheets, and hollow microspheres.[10,13] Further-
With ever-growing demand in automotive and stationary more, to overcome the hurdles of poor electrical conductivity,
energy storage applications, devices that can be recharged many strategies have been contrived to ameliorate the rate
swiftly, have long lifetime and high capacitance, and are inex- capability of LTO by means of elemental doping[14] and surface
pensive, are highly desirable.[1] Li-ion batteries (LIBs) have been modification with highly conductive substances.[15–24] Although
a favorable power source device in electronics and electrical LTO-based nanomaterials have been extensively studied for
vehicles because of the high capacity and long cycle life. Never- LIBs, their application to NIBs has been less explored so far.
theless, since it is envisioned that the lithium supply may run LTO nanorods, carbon coated LTO nanowires, and LTO mate-
out due to the increasing demand, sodium-ion batteries (NIBs) rials with hierarchically porous structures have recently been
as a promising candidate have again aroused intensive interest synthesized and demonstrated to deliver good sodium ion
due to more abundant and inexpensive sodium resources.[2–4] storage performance.[8,25,26] In spite of these improvements,
Despite efforts in developing the suitable new electrode they still are insufficient in practice and the major problems of
NIBs are fast capacity fading and poor high-rate performance.
In this respect, rational nanoscale surface engineering of elec-
G. B. Xu, Prof. L. W. Yang, Dr. X. L. Wei, troactive nanoarchitectures is a viable means to enhance the
Prof. J. W. Ding, Prof. J. X. Zhong properties.[27]
Hunan Key Laboratory of Micro-Nano
Energy Materials and Devices 2D nanosheets less than 10 nm are promising in high-per-
School of Physics and Optoelectronics formance batteries because of the short paths enabling fast
Xiangtan University ion diffusion, large exposed surface, as well as abundant ion
Hunan 411105, China insertion channels.[28,29] Ultrathin LTO nanosheets with a larger
E-mail: ylwxtu@xtu.edu.cn
specific surface area often have a larger discharge capacity
Prof. L. W. Yang, Prof. P. K. Chu
Department of Physics and Materials Science
and improved rate capability due to unprecedented pseudo-
City University of Hong Kong capacitive effect as the electrochemical interaction takes place
Tat Chee Avenue on the surface[30,31] or increased storage site resulting from the
Kowloon, Hong Kong, China cooccupation at the 8a and 16c sites at the surface region of
E-mail: paul.chu@cityu.edu.hk spinel structure.[14,32,33] Recently, 0D/2D heterostructure mate-
DOI: 10.1002/adfm.201505435 rials have attracted much attention in photomodulation and

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 www.afm-journal.de
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Figure 1. Schematic showing the synthesis of the heterostructure composite composed of (designated as LTO-MoS2-2) delivers the best
ultrasmall MoS2 QDs and ultrathin LTO nanosheets. The vacuum-filtration assisted assembly electrochemical performance.
process enables facile and controllable integration of ultrathin LTO nanosheets and ultrasmall
MoS2 QDs. “D” and “S” represent the diffusion-controlled and enhanced surface-controlled
lithium/sodium storage behavior, respectively.
photodetection.[34] For example, in the MoS2 monolayers doped
with graphene quantum dots (QDs), abnormal photolumines-
cence (PL) tuning was observed due to the competition between
the photogenerated exciton and charge exciton induced by
charge transfer at the 0D/2D multilayer interface.[34] However,
the application of the heterostructures formed from 0D/2D
materials to energy storage has been rarely reported, although
MoS2 QDs have value-adding functions for solar cells, hydrogen
evolution, intracellular microRNA detection, and multiphoton
bioimaging as a result of quantum confinement and edge
effects.[35] Herein, the heterostructured composite of MoS2
QDs and LTO nanosheets is prepared by self-assembly and the
Li/Na storage properties are assessed. The LTO nanosheets
homogeneously anchored with ultrasmall MoS2 QDs possess
enhance surface-controlled Li/Na storage behavior, rendering
the resulting heterostructure composite with outstanding Li/Na
storage properties such as high capacity and high-rate capability
as well as excellent cycling stability.
2. Results and Discussion
As shown in Figure 1, the synthesis of LTO/MoS2 heterostruc-
tured composite involves the preparation and vacuum-filtration
assisted assembly of MoS2 QDs and LTO nanosheets. In brief,
a simple and mild oxidant(H2O2)-triggered spontaneous exfolia-
tion process is employed to prepare the ultrasmall MoS2 QDs
in N-Methyl-2-pyrrolidinone(NMP).[35] Then highly-crystalline
ultrathin LTO nanosheets prepared via topotactic transfor-
mation of layered ultrathin Li1.81H0.19Ti2O5·xH2O (H-LTO)
nanosheets with a minute of gadolinium ions at 700 °C[14]
are added into the NMP solution with ultrasmall MoS2 QDs.
Once being introduced, the MoS2 QDs tend to reside on the
surface of energetically more stable LTO nanosheets by van der
Waals force to make the total free energy of solution system
being minimized. After being stirred for about 1 h, the solu-
tion is vacuum-filtered with a microporous filtering mem-
brane with pore size of 0.15 µm and after being dried at 50 °C
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under vacuum, the LTO/MoS2 composite is
prepared. In our experiments, the loading
amounts of MoS2 QDs have important influ-
ence on electrochemical performance of
the LTO/MoS2 heterostructure composite.
As shown in the inset in Figure 2 and
Figure S1a (Supporting Information),
the LTO/MoS2 heterostructure composite
becomes darker with more MoS2 QDs,
implying that the MoS2 QDs are interspersed
homogeneously in the LTO nanosheets. The
cycling performances of the LTO/MoS2 heter-
ostructure composite with different amount
of MoS2 QDs as shown in Figure S1b (Sup-
porting Information) reveal that the sample
prepared with 2.5 wt% MoS2 QDs in NMP
The phase structures of the materials are
characterized by powder X-ray diffraction
(XRD). As depicted in Figure 2, the diffrac-
tion peaks of the as-prepared LTO nanosheets are well indexed
to cubic spinel LTO with space group of Fd-3m (JCPDS No.
49-0207). The sharp and well-defined peaks suggest high crys-
tallinity and no other peaks such as TiO2 can be detected indi-
cating high purity as well. Compared to the LTO nanosheets,
three weak peaks at 14.3°, 39.4° and 49.7° originating from
the ultrasmall MoS2 QDs, which are well consistent with
hexagonal MoS2 (JCPDS No. 77-1716), can be observed. The
crystal structure of the ultrasmall MoS2 QDs, LTO nanosheets,
and LTO-MoS2-2 composite is further characterized by trans-
mission electron microscopy (TEM). The typical TEM image
in Figure 3a shows that the as-made MoS2 QDs are well-dis-
persed and have a size of about 3 nm. The characteristic (101)
lattice plane of hexagonal MoS2 (PDF No. 37-1492) with a lat-
tice spacing of 0.27 nm can be well resolved in high resolu-
tion TEM image (HRTEM) (Figure 3b), suggesting high crys-
tallinity of the MoS2 QDs. The ultrasmall MoS2 QDs solution
Figure 2. XRD patterns of the LTO nanosheets and LTO-MoS2-2 com-
posite and the related photographs.
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Figure 3. a) TEM image of MoS2 QDs with the size distribution in the inset; b) HR-TEM image of MoS2 QDs; c) Photographs of the MoS2 QDs solu-
tion taken under visible light (left) and 365 nm UV light (right) illumination; d,f) Typical TEM and HR-TEM images of the LTO nanosheets as well as
corresponding e) SAED patterns; g,h) typical TEM and HR-TEM images of the LTO-MoS2-2 composite.

is very stable without any noticeable precipitation after several
weeks at room temperature. The solution under illumination
by a 365 nm lamp shows intense blue fluorescence (Figure 3c)
consistent with the strong quantum confinement effect.[35]
Figure 3d shows typical TEM image of the LTO nanosheets,
demonstrating that the sample retains the sheet-like feature of
the H-LTO precursor with a thickness of 10 nm, which is con-
sistent with our previous results.[24] The representative SAED
patterns (Figure 3e) and HRTEM image (Figure 3f) suggest
single crystallinity of individual LTO nanosheet. Well-defined
lattice fringes with a separation of 0.48 nm in the HRTEM
image correspond to the spacing of the (111) atomic planes
of spinel LTO. Figure 3g shows the typical TEM image of the
LTO-MoS2-2 composite, indicating that the ultrasmall MoS2
QDs are dispersed well on the surface of LTO nanosheets.
Figure 3h is the corresponding HRTEM image disclosing that
besides the lattice fringes of the LTO nanosheets, a few black
spots with a size of about 3 nm originating from the ultrasmall
MoS2 QDs can be observed. Although it is rather difficult to
obtain clear lattice fringes of the MoS2 QDs due to the influ-
ence of the LTO nanosheets, the presence of MoS2 QDs can
be corroborated by Raman scattering and XPS to be discussed
later.
Figure 4a depicts the Raman spectra acquired from the LTO-
MoS2-2 composite. The Raman peaks at 670, 431, 348, 262, and
234 cm−1 are five characteristic phonon modes (A1g+Eg+3F2g)
of cubic spinel LTO, which are consistent with those from LTO
nanosheets. The low-frequency Raman bands (F2g) at 340, 268,
and 234 cm−1 originate from the vibration of lithium octahe-
drally coordinated by oxygen. The band at 431 cm−1 (Eg) is the
stretching mode of Li-O in the LiO4 tetrahedra and the one at
670 cm−1 (A1g) is the stretching mode of Ti-O covalent bonding
in the TiO6 octahedra. Besides, these Raman modes from cubic
spinel LTO, two characteristic peaks at 383.8 and 409.4 cm−1
ascribed to the in-plane E12g and out-of-plane A1g modes of
MoS2,[35] respectively, are observed from the LTO-MoS2-2 com-
posite. Furthermore, the A1g phonons soften (redshift) while the
A1g phonons stiffen (blueshift) from the LTO-MoS2-2 composite
compared to bulk MoS2. The results imply that the thickness of
MoS2 QDs is thinned to fewer layers.[36] The surface electronic
states and chemical composition of the LTO-MoS2-2 composite
are determined by X-ray photoelectron spectroscopy (XPS).

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Figure 4. a) Raman spectra of LTO-MoS2-2 composite and LTO nanosheets; b) survey XPS spectrum of the LTO-MoS2-2 composite; c,d) high-resolution
Mo 3d and S 2p XPS spectra of the LTO-MoS2-2 composite.
The results presented in Figure 4, Figures S2 and S3 (Sup-
porting Information), reveal the existence of Li, Ti, O, Mo, and
S with a stoichiometric Mo/S atomic ratio of about 1:2. Quan-
titative XPS reveals that the detectable Mo content of ≈1 wt%
is below the 2.5 wt% of the MoS2 QDs in NMP. The two peaks
at 228.6 and 231.8 eV attributed to Mo 3d5/2 and Mo 3d3/2,
respectively and due to Mo4+ in pure MoS2[35,37] are observed
from high-resolution Mo 3d spectrum(see Figure 4c). The high-
resolution S 2p peaks at 161.3 and 169.0 eV represent sulfide.
It should be pointed out that the binding energy of Mo4+ in the
LTO-MoS2-2 composite shifts toward low-energy direction com-
pared with that previously reported,[37] suggesting strong elec-
tron interaction between the LTO nanosheets and coupled MoS2
QDs.[38] Based on aforementioned results, ultrasmall MoS2
QDs with good crystallinity are successfully coupled with LTO
nanosheets and the highly dispersed MoS2 QDs on the LTO
nanosheets benefit the formation of LTO/MoS2 heterojunctions
which are expected to exhibit unique Li/Na storage behavior,
thereby enhancing energy storage performance of the electrode
materials.
For exploring the benefits granted by nanoscale LTO/MoS2
heterojunctions, the obtained composites as LIB and NIB
anode materials are investigated using CR2032- type coin cells.
Figure 5a shows the CV curves of the LTO-MoS2-2 electrode
at different sweeping rates in the potential range between 1.0
and 2.5 V (vs Li/Li+). The well-defined and symmetrical redox
peaks are observed, indicating excellent electrode kinetics of the
LTO-MoS2-2 electrode. Interestingly, the LTO-MoS2-2 electrode
exhibits much broader redox peaks with higher peak currents
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(i) at every sweep rate (v) compared to the LTO nanosheets elec-
trode (see inset of Figure 5a). The broadening of the CV peaks
is different from those observed in graphene QDs coated VO2
arrays[27] and CuO nanowires[39] as well as LTO nanosheets
modified with Ag nanocrystals,[24] in which the main role of the
graphene QDs and Ag nanocrystals is to reduce the electrode
polarization of electrode materials. The results imply another
lithium storage process in the LTO-MoS2-2 electrode. Each of
broad anodic or cathodic peaks includes two overlapped peaks
(or a shoulder) in LTO-MoS2-2 electrode, which can be decon-
voluted into two pairs of redox peaks. Compared with these of
LTO nanosheets, for example, at the sweep rate of 1 mV s−1 as
shown in Figure S4 (Supporting Information), the redox peaks
at 1.74 and 1.41 eV are mainly attributed to the redox reaction
of Ti4+/Ti3+, respectively, associated with lithium insertion/
extraction in spinel LTO lattice, which are consistent with those
reported for other LTO-based materials.[18,33] The redox peaks
at 1.81 and 1.36 eV cannot be attributed to lithium insertion/
extraction into MoS2 because lithium extraction from MoS2
would exhibit an anodic peak located at around 2.3 V due to
the oxidation of Mo into MoS2.[40] Therefore, this pair of redox
peaks should originate from the coupling of MoS2 QDs and
LTO nanosheets. The results also indicate that the coupled
MoS2 QDs speed up lithium diffusion and increase lithium
storage capacity. Differing from the results for LIBs, the peaks
corresponding to sodium insertion/extraction of LTO exhibit no
obvious broadening in the CV curve of the LTO-MoS2-2 com-
posite (see Figure 5b). This likely originates from the broad and
inconspicuous redox peaks of the LTO for NIBs.[8] In general,
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(a) (b)

(c) (d)

(e) (f)

Figure 5. a,b) CV curves of the LTO-MoS2-2 composite and LTO nanosheets (see inset) at various scanning rates for LIBs and NIBs; c,d) determina-
tion of the b-value of the LTO-MoS2-2 composite and LTO nanosheets electrodes for LIBs and NIBs using the relationship between the peak current
(i) and scanning rate (v) in (a) and (b) according to i = avb; e,f) Nyquist plots of the LTO-MoS2-2 composite and LTO nanosheets for LIBs and NIBs
after 100 discharging and charging cycles.

the currents (i) in the CV curves of active electrode materials
response to the sweeping rates (v) obeying a power law rela-
tionship of i = avb, where a and b are adjustable values.[5,41]
A b-value of 0.5 indicates that the current is a typical battery
behavior controlled by semi-infinite linear diffusion, and the b
value of 1 implies that the current is proportional to the sweep
rate, revealing surface-controlled charge storage processes.
Figure 5c,d presents the log(v)-log(i) plots for the LTO-
MoS2-2 composite and LTO nanosheets as electrode materials
in LIBs and NIBs. The fitted b values for cathodic and anodic
peak currents in the LTO-MoS2-2 composite (0.70 and 0.71
for LIBs, 0.70/0.65 for NIBs) are larger than those of the LTO
nanosheets (0.58 and 0.59 for LIBs, 0.44/0.60 for NIBs). The
unique phenomena observed from the LTO-MoS2-2 composite
suggest two points. First, there is more contribution from sur-
face-controlled Li/Na storage that behaves similarly to pseudo-
capacitive effect in supercapacitor materials for the LTO-MoS2-2
composite and it is expected to ameliorate high-rate capability
and cycling stability.[5] The surface-controlled capacitive contri-
bution is also determined using another analysis, in which the
current at a particular voltage is considered to contain contribu-
tions from capacitive (k1) and diffusion (k2) controlled processes
according to following equation,[42] i = k1v + k2v1/2. The amount
of charge stored due to the capacitive controlled process at a
typical scan rate is presented in Figure S5 (Supporting Informa-
tion), which further confirm the enhanced surface-controlled
Li/Na storage in the LTO-MoS2-2 composite compare to LTO
nanosheets. Second, the enhanced surface-controlled storage
behavior of the H-LTO-MoS2 composite is attributed to the
hetero-interface effect between the LTO nanosheets and MoS2
QDs. It is proposed that the change of structural environments
in the near-surface region of LTO results in a distribution of
redox potentials in the near-surface area due to surface-related
lithium storage or the cooccupation at the 8a and 16c sites at
the surface region.[43] This unique effect becomes increasing
dominated when the size is reduced to 10 nm.[9] In our case, on

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(a) (b)

(c) (d)

(e) (f)

Figure 6. a,b) Charging–discharging voltage profiles of the LTO-MoS2-2 composite and LTO nanosheets as LIBs electrodes for the 1st, 500th, and
1000th cycles at a current rate of 10 C; c,d) charging–discharging voltage profiles of the LTO-MoS2-2 composite and LTO nanosheets as LIBs elec-
trodes at different current rates; e) corresponding rate capabilities at different current rates from 1 C to 30 C for the LTO-MoS2-2 composite and
LTO nanosheets; f) corresponding long-cycling performance and Coulombic efficiency versus cycle number of the LTO-MoS2-2 composite and LTO
nanosheets at a rate of 10 C.

account of band alignment and potential difference resulting
from intrinsic band gap properties of MoS2 and LTO, the strong
hetero-interfacial effect between the LTO nanosheets and cou-
pled MoS2 QDs produces the space charge layer near the LTO/
MoS2 interface to seriously change the structural environ-
ments in the near-surface region of LTO nanosheets, leading
to a distribution of redox potentials in the near-surface area
accompanying enhanced surface-controlled Li/Na storage. The
hetero-interfacial effect likely also enhances the relative current
associated with high surface electrochemical activity within the
surface reaction region. In other words, this hetero-interfacial
effect makes the gradients of the Li/Na concentrations during
Li/Na insertion/extraction being suppressed notably within the
space charge layer near the LTO/MoS2 interface, and subse-
quently the diffusion distance for Li/Na ions is notably short-
ened in the LTO/MoS2 heterostructure to allow Li/Na ions to
migrate more quickly throughout the LTO nanosheets, thereby
eradicating the structural and interfacial instability of the LTO
due to the surface reconstruction or mechanical failure associ-
ated with too high surface Li/Na storage[43] and enhancing the
cycling stability. In addition, the nanocavities between the cou-
pled MoS2 QDs offer favorable transport routes for Li/Na ions
and simultaneously provide a nontrivial contribution to the
capacity due to physical adsorption of Li/Na ions between the
MoS2 QDs.
Figure 6a,b shows the galvanostatic charging–discharging
profiles of the LTO nanosheets and LTO-MoS2-2 composite
electrodes for the 1st, 500th, and 1000th cycles at a current rate
of 10 C in the voltage range from 1.0 to 2.5 V versus Li/Li+.
Both electrodes exhibit similar charging and discharging flat
plateaus at around 1.5 V, confirming characteristic two-phase
lithium insertion/extraction reaction mechanism of spinel
LTO.[22,44] However, the charging/discharging voltage profiles
of the LTO-MoS2-2 composite electrode have a flatter profile

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than those of the reference LTO nanosheets for every cycle,
suggesting smaller polarization (Δ E) between the charging
and discharging plateaus. The lower electrochemical polariza-
tion implies improved reaction kinetics due to higher surface
electron conductivity of unique LTO/MoS2 heterostructure.
On the one hand, an extended solid solution region for Li+
insertion into LTO is observed from the LTO-MoS2-2 com-
posite electrode in the charging–discharging voltage profiles
from ≈2.3 to ≈1.5 V, similar to those reported previously from
small particles such as TiO2[45,46] and Si,[5] in which an addi-
tional surface lithium storage mechanism exists. On the other
hand, a smaller slope below 1.5 V that is a typical feature of
a supercapacitor is observed from the LTO-MoS2-2 composite
electrode, implying higher capacitance associated with lithium
storage by surface control of the LTO/MoS2 heterostructure.
The rate capability of the LTO-MoS2-2 composite as an anode
for LIBs is investigated by charging–discharging at various
current rates from 1 to 30 C (see Figure 6c,d). The Δ E of the
LTO-MoS2-2 composite electrode is depressed compared to the
LTO nanosheet electrode for every C-rate, suggesting better rate
capability. At 1 C, the LTO-MoS2-2 composite electrode has a
discharge capacity of 189 mAhg−1, which is beyond the theoret-
ical value of 175 mAh g−1 suggesting that there exist additional
lithium storage sites in the LTO-MoS2-2 composite electrode.[47]
As the rates is increased from 1 to 5 ,10, 20, and 30 C, the dis-
charge capacities are 177, 172, 166, and 161 mAhg−1 with the
capacity retention of 93.6% , 91% , 88%, and 85.1%, respec-
tively. In comparison, the LTO nanosheets electrode cannot
match such high capacity retention at every rate. For example,
the capacity of the LTO nanosheets at 30 C is only 120 mAhg−1,
which is ≈68.8% of that at 1 C. More importantly, as shown in
Figure 6e, the relative increase (Δ C) of discharge capacity is
larger at higher rates and the Coulombic efficiencies at large
rates approach 100% for each cycle, implying ultrafast lithium
diffusion and high reversibility of electrochemical reaction due
to heterostructure effect in the LTO-MoS2-2 composite elec-
trode, thereby leading to excellent rate capability. In addition,
a stable capacity of 178 mAhg−1 with negligible loss for subse-
quent cycling can be retained when the current rate is returned
to 1 C after the rate capability test, suggesting superior sta-
bility of the LTO/MoS2 heterostructure. Figure 6f displays the
long-term cycling performance of the LTO-MoS2-2 composite
electrode at a high current density of 10 C, demonstrating a
stable capacity of 170 mAhg−1 with the Coulombic efficiency
approaching 100% after 20 cycles. A capacity of 160 mAh g−1
is still retained after 1000 cycles with a capacity loss of only
5.9%. The cycling performance of the LTO-MoS2-2 composite
electrode is superior to that of the LTO nanosheets with a
capacity loss of 15.8% after 1000 cycles and the cycling stability
(0.0059% decay per cycle) of the LTO-MoS2-2 composite elec-
trode is among the best observed from LTO-based anodes so
far. The high-rate and long-term cycling performance of the
LTO-MoS2-2 composite electrode are comparable to the results
obtained from LTO nanowire arrays,[20] Cu-doped LTO-TiO2
nanosheets,[48] self-supported LTO nanosheets arrays,[32] LTO-C
nanotube arrays,[18] carbon-encapsulated F-doped LTO,[19] LTO
tailored by cathodically induced graphene[22] (see Table S1 in
the Supporting Information), and so on, confirming the posi-
tive effects rendered by the LTO/MoS2 heterostructure.
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Owing to the aforementioned advantages of MoS2 QDs cou-
pling, we further examine the sodium storage performance
of the LTO/MoS2 heterostructure composite. As shown in
Figure 5b, the CVs between 0.5 and 2.5 V acquired from both
the LTO-MoS2-2 composite and LTO nanosheets show one
anodic peak at 1.09 V and cathodic peak at 0.66 V representing
sodium insertion-extraction in the LTO crystal lattice. A pair of
weak anodic and cathodic peaks is observed at around 0.9 V
implying that the Na+ extraction process follows a more com-
plicated path.[8] Figure 7a,b depict the charging–discharging
voltage profiles of the LTO nanosheets and LTO-MoS2-2 com-
posite electrodes cycled at different current rates from 0.1 to
5 C between 0.5 and 2.5 V. Both electrodes exhibit the same
features in the curves: a slow voltage decay from 1.5 to 0.8 V
and a flat plateau from 0.8 to 0.5 V consistent with the CV
results. The region of the slow voltage decay from 1.5 to 0.8 V
is extended for the LTO-MoS2-2 composite electrode indicating
an enhanced surface Na storage behavior. The polarization
between the charging and discharging plateaus of the LTO-
MoS2-2 composite electrode is smaller than that of the refer-
ence LTO nanosheets suggesting a better rate capability as well.
For example, as shown in Figure 7c, at rates of 2 and 5 C, the
capacities of the LTO-MoS2-2 composite electrode are 118 and
91 mAh/g and greater than those of the LTO nanosheets elec-
trode of 73 and 49 mAh/g, respectively. The cycling stability is
investigated at 2 C for 200 cycles and Figure 7d shows that the
reversible capacity of the LTO-MoS2-2 composite electrode can
be retained at 101 mAhg−1 after 200 cycles, which is superior to
that (60 mAhg−1) of the LTO nanosheets. These results demon-
strate that the LTO/MoS2 heterostructure composite is suitable
for high-power NIBs due to excellent stable capacity and high
rate capacity.
The superior Li/Na storage performance of the LTO/MoS2
heterostructure composite can be attributed to some enhance-
ments of transport kinetics in electrode. To understand the
transport kinetics in the LTO-MoS2-2 composite electrode, elec-
trochemical impedance spectra (EIS) are performed after the
100th cycling test. The obtained Nyquist plots are presented
in Figure 5e,f, revealing a purely resistive response at high
frequency region represented by the ohmic resistance (Rs) of
the electrode and electrolyte, a semicircle arc due to the charge-
transfer resistance (Rct) on electrode–electrolyte interface in
high-to-middle frequency region and an inclined straight line
ascribed to the Warburg impedance (Rw) in low frequency
region. The Warburg-like response manifests larger slopes for
the LTO-MoS2-2 composite electrodes for both LIBs and NIBs
suggesting higher Li/Na mobility[19] and enhanced pseudoca-
pacitive properties compared to the LTO nanosheets.[49] The
semicircle arcs of the LTO-MoS2-2 composite electrode for
both LIBs and NIBs are smaller than those of reference LTO
nanosheets, implying smaller Rct values at the electrode–elec-
trolyte interface,[22,47] which are consistent with the simulation
results (see Table S1 in the Supporting Information) using
modified Randles equivalent circuit (see Figure S6 in the Sup-
porting Information). The results indicate that the LTO/MoS2
heterostructure facilitates rapid charge transfer at the electrode/
electrolyte interface in the LTO-MoS2-2 composite electrode,
thereby leading to better Li/Na storage capability. Further-
more, the indicative exchange current density can be analyzed
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FULL PAPER

(a) (b)

(c) (d)

Figure 7. a,b) Charging–discharging voltage profiles of the LTO-MoS2-2 composite and LTO nanosheets as NIBs electrodes at different current rates;
c) corresponding rate capabilities at different current rates from 0.1 C to 5 C for the LTO-MoS2-2 composite and LTO nanosheets electrodes; d) long
cycling performance of the LTO-MoS2-2 composite and LTO nanosheets as NIBs electrode at a rate of 2 C.

according to the equation of i0 = RT/nFRct (see Table 1).[19] The
enhanced exchange current density of the LTO-MoS2-2 com-
posite electrode for NIBs is not as obvious as that of LIBs due
to slow Na+ diffusion in the LTO host. However, the exchange
current density of the LTO-MoS2-2 composite electrode for LIBs
after 100 cycles is nearly double that of the LTO nanosheets
electrode (i0 = 0.84 versus 0.41 mAcm−2). The enhancement in
the charge-transfer kinetics in the LTO-MoS2-2 composite elec-
trode results from the special structure of the LTO/MoS2 het-
erostructure. First, the heterostructure combination of the LTO
nanosheets and MoS2 QDs promotes Li/Na insertion–extrac-
tion due to the shorter Li+/Na+ diffusion distance and higher
surface electrochemical activity associated with the coupled het-
erointerfacial effect between LTO nanosheets and MoS2 QDs as
well as avoiding the drawback of grain boundaries benefiting
from the singe-cryastal nature of LTO nanosheets. Second,
the structure stability is better since the formation of covalent
bonds between the MoS2 QDs and LTO during the electro-
chemical reactions can act as an effective buffer to eradicate
the structural and interfacial instability of the LTO due to the
surface reconstruction or mechanical failure associated with too
high surface Li/Na storage behaviors.[43] The homogeneously
coupled MoS2 QDs can also prevent dissolution of the LTO by
decreasing the exposed surface area of the LTO. In addition to
promoting Li/Na insertion–extraction accompanying enhanced
surface-controlled Li/Na storage during the electrochemical
reactions, the “sensitization” effect of the coupled ultrasmall
MoS2 QDs likely makes the LTO nanosheets surface lipophilic
thereby facilitating electrolyte penetration and ion transfer to
improve the reaction kinetics.[27] Consequently, outstanding
Li/Na storage properties such as excellent rate capability and
remarkable cycling stability are achieved from the LTO/MoS2
composite.
3. Conclusion
High capacity, high rate, and durable Li/Na storage are achieved
from the heterostructure composite composed of single-crystal
LTO nanosheets homogeneously anchored with ultrasmall
MoS2 QDs. The strong hetero-interfacial effect between the LTO
nanosheets and MoS2 QDs endows the 0D/2D heterostructure

Table 1. Rs and Rct values of the LTO nanosheets and LTO-MoS2-2 composite for LIBs and NIBs after 100 cycles in half-cells according to Figure 5e,f
as well as exchange current density (i0) calculated from to i0 = RT/nFRct, where n and F are constants.

Samples LIBs NIBs

Rs [Ω] Rct [Ω] i0 [mA cm−2] Rs [Ω] Rct [Ω] i0 [mA cm−2]
LTO 5.13 62.1 0.41 5.01 202 0.123
LTO-MoS2-2 4.21 30.2 0.845 4.66 161 0.154

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with enhanced surface-controlled Li/Na storage. The MoS2
QDs may work as a surface sensitizer and protector. As a
result, the LTO/MoS2 heterostructure composite possesses
outstanding Li/Na storage properties. With regard to lithia-
tion, the LTO/MoS2 heterostructure composite shows a stable
reversible specific capacity of 170 mAhg−1 after 20 cycles and it
is maintained at 160 mAhg−1 after 1000 cycles at a high rate of
10 C with 94.1% retention. During sodiation, a high capacity of
91 mAh/g at a rate of 5 C and superior capacity retention with
101 mAhg−1 after 200 cycles at the rate of 2 C are achieved. The
results provide an effective strategy to improve the capacity, rate
capability, and cycling stability of LTO-based anode material for
LIBs and NIBs, thus pushing LTO as a cost-effective alternative
for next-generation high-performance electrochemical energy
storage devices.
4. Experimental Section
Synthesis of Ultrathin LTO Nanosheets and Ultrasmall MoS2 QDs: The
ultrathin LTO nanosheets were prepared by a modified hydrothermal
method followed by annealing treatment.[24] The ultrasmall MoS2
QDs were prepared by a spontaneous mild oxidant (H2O2)-triggered
exfoliation process.[35] Typically, 200 mg of pristine MoS2 flake were
dispersed in a solution of H2O2 (30 wt% aqueous solution) and NMP
(v/v = 1:1) and stirred at 35 °C for 10 h. The mixture was centrifuged for
30 min at 5000 rpm and the upper half of the supernatant was collected.
After centrifugation for two to four times, the mixture became colorless
and the ultrasmall MoS2 QDs dispersed in NMP were obtained.
Synthesis of the LTO/MoS2 Composite: Since it was rather difficult
to collect the ultrasmall MoS2 QDs powder, the MoS2 QDs dispersed
in NMP were used to prepare the LTO/MoS2 composite directly.
First, the ultrathin LTO nanosheets with an appropriate content were
added slowly to the NMP solution with ultrasmall MoS2 QDs. After
being stirred for about 1 h, the solution was vacuum-filtered through
a microporous filtering membrane with a pore size of 0.15 µm. The
collected samples were dried at 50 °C for 10 h in vacuum to remove
residual NMP molecules to obtain the LTO-MoS2 composite. To adjust
the content of MoS2 QDs in the composite, the NMP solutions with
different concentrations of MoS2 QDs (1, 2.5, 5, and 10 wt%) were
prepared by evaporating the NMP content. These samples were
designated as LTO-MoS2-1, LTO-MoS2-2, LTO-MoS2-3, and LTO-MoS2-4,
respectively.
Materials Characterization: The morphology, microstructure, and
composition of the samples were studied by SEM (Hitachi, S4800), TEM
(JEOL-2100F) equipped with SAED, and XRD (Rigaku, D/MAX 2500)
using a copper Kα radiation source (λ = 0.154 nm), Raman scattering
(Renishaw InVia system at an excitation wavelength of 532 nm), and
XPS (Kratos Analytical Ltd., UK) using an Al Kα source.
Electrochemical Characterization: The electrochemical tests were
conducted using two-electrode CR2032 type coin cells. The working
electrodes in the lithium and sodium cells were prepared by pasting the
mixture of the active materials, carbon black, and polyvinylidene fluoride
(PVDF) at a weight ratio of 8:1:1 onto a Cu foil. After being dried at 80 °C
for 6 h in air and then at 120 °C in vacuum for 12 h, the electrodes
were punched into round disks with a diameter of 1.2 cm and the mass
of the active materials ranging from 1 and 2 mg. Metallic lithium and
sodium foils were used as the counter electrodes, and Celgard 2400
polypropylene and glass fiber (Whatman GF/D) as separators for the
lithium and sodium cells, respectively. The electrolytes were 1 M LiPF6
in a 1:1 (V:V) mixture of ethylene carbonate/dimethyl carbonate and 1 M
NaClO4 in 1:1 (V:V) mixture of ethylene carbonate/propylene carbonate
for lithium and sodium cells, respectively. All coin cells were assembled
in an Ar-filled glove box. The galvanostatic charging/discharging was
performed using a multichannel battery test system (NEWARE BTS-610)
Adv. Funct. Mater. 2016, 26, 3349–3358 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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in the voltage range from 1 to 2.5 V (vs Li/Li+) and 0.5 to 2.5 V (vs Na/
FULL PAPER
Na+). Cyclic voltammetry (CV) was carried out on an electrochemical
workstation (CHI660D) in the voltage range between 1 and 2.5 V (vs Li/
Li+) as well as 0.5 and 2.5 V (vs Na/Na+). Electrochemical impedance
spectroscopy (EIS) was performed between 0.01 Hz and 100 kHz on the
CHI660E electrochemical workstation. All the tests were conducted out
at room temperature.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (Grant Nos. 11474242, 51272220, 11374252, and
51472209), Program for Changjiang Scholars and Innovative Research
Team in University (Grants No. IRT13093), as well as City University of
Hong Kong Applied Research Grant (ARG) No. 9667104.
Received: December 16, 2015
Revised: January 27, 2016
Published online: March 2, 2016
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