Applied Surface Science 534 (2020) 147679

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Efficient TiC-C hybrid conductive matrix for ZnTe anode in Lithium-ion T

storage
Quoc Hai Nguyena,1, , Quoc Hanh Nguyenb,1, Seongjoon Sob, Jaehyun Hurb,
⁎ ⁎

a
Biomaterials and Nanotechnology Research Group, Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City 700000, Viet Nam
b
Department of Chemical and Biological Engineering, Gachon University, Seongnam, Gyeonggi 461-701, Republic of Korea

ARTICLE INFO ABSTRACT

Keywords: ZnTe alloy is simply prepared by the primary annealing step, along with the formation of TiC-C hybrid con-
ZnTe ductive matrix in the secondary ball-milling process. As-prepared ZnTe@TiC-C nanocomposite consists of active
TiC ZnTe nanocrystallites embedded in a TiC-C buffering material, which is adopted as a potential anode material for
Anode Lithium-ion storage. In comparison with stand-alone carbon matrix as a buffering material, the presence of the
Ball milling
TiC-C hybrid matrix improves the electrochemical performances of ZnTe active material in terms of capacity,
LIBs
stability, reversibility, and rate capability performances. Also, the optimum content of TiC in the ZnTe@TiC-C
composites is evaluated based on the electrochemical performances, in that the ZnTe@TiC(20%)-C composite
exhibits the highest reversible capacities of ~547 mAh g−1 after 300 cycles at 0.1 A g−1, the good rate capability
(84% capacity retention at 10 A g−1 when compared with the capacity at 0.1 A g−1), and the cycle life at 1 A
g−1 (~700 mAh cm−3 after 500 cycles). The enhanced electrochemical performance of the ZnTe active material
with the presence of the TiC-C hybrid matrix can be attributed to the effective mitigation against the large
volume change in the ZnTe and the high conductivity, thereby facilitating electron transport during prolonged
cycling.

1. Introduction
Owing to the outstanding properties such as high capacities, high
power densities, long cycle life, low self-discharge, and no memory
effect, lithium-ion batteries (LIBs) are still attracting much attention as
one of the most important rechargeable batteries in various commercial
applications [1–11]. To enhance the electrochemical performance of
LIBs that could meet the requirements for the next generation batteries,
the anode materials have been significantly improved with main fo-
cuses on overcoming some drawbacks including low capacity, cyclic
instability, and poor rate capability. Although graphite has been widely
used as a stable and low-cost anode material for LIBs, this material
presents major drawbacks, which include a limited theoretical specific
capacity (~372 mAh g−1), low rate capability, and safety issues (Li
plating) [12–15]. To overcome these limitations, most researches have
been directed toward the exploration of new materials for the realiza-
tion of high-performance anodes [16–21].
Recently, Li-alloying materials such as Li-Sn, [22–24] Li-Si, [25–27]
Li-Sb, [28–31] Li-P, [32–35], and Li-Ge [36] have been proposed as
potential anode materials for the next generation LIBs due to a large
number of Li+ ions coordinated with electrode materials during the
alloying/dealloying reactions as well as the reduced safety concerns
associated with their high reaction potentials. Among various Li-al-
loying-based materials, zinc-based materials have been studied as po-
tential anodes in LIBs due to the cost-effectiveness, eco-friendliness, and
the natural abundance of Zn. Zn not only exhibits a very high volu-
metric capacity (~1511 mAh cm−3 corresponding to the theoretical
gravimetric capacity of 410 mAh g−1) but also easily form various Zn-
metal binary alloying compounds such as Zn-Sb, Zn-S, Zn-P, Zn-Se, and
Zn-Te, among others [37–48]. However, Zn-based anode materials de-
monstrate poor electrochemical performances, as they undergo sig-
nificant changes in volume and particle agglomeration during electro-
chemical cycling [20,21]. Moreover, in several studies, it was reported
that Te, which is a chalcogen group element, can alloy with Li to form
Li2Te with a theoretical capacity of 420 mAh g−1 [49–51]. Even though
Te exhibits a relative lower gravimetric capacity when compared with
the atoms of other chalcogen group elements, e.g., S (1675 mAh g−1)
and Se (678 mAh g−1), it has an high theoretical volumetric capacity of
~2621 mAh cm−3 due to its high density (6.24 g cm−3), which is al-
most higher than that of S by a factor of 3. Furthermore, Te exhibits a

⁎
Corresponding authors.
E-mail addresses: nguyenquochai@tdtu.edu.vn (Q.H. Nguyen), jhhur@gachon.ac.kr (J. Hur).
1
Q. H. Nguyen and Q. H. Nguyen contributed equally to this work.

https://doi.org/10.1016/j.apsusc.2020.147679
Received 8 June 2020; Received in revised form 13 August 2020; Accepted 24 August 2020
Available online 26 August 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
Q.H. Nguyen, et al.
higher electronic conductivity (2 × 10−4 MS m−1) than those of Se
(1 × 10−10 MS m−1) and S (5 × 10−22 MS m−1) [50]. Therefore, the
combination of Zn and Te with respect to the formation of a bimetallic
alloying compound (ZnTe) is an effective strategy for the realization of
a potential anode for LIBs, thus utilizing their high capacities (theore-
tical capacity of 416 mAh g−1) and conductivities. In addition, the
distinct reaction potential between Zn and Te in ZnTe allows for se-
quential lithiation, which mitigates the large and abrupt change in
volume during cycling (theoretical volume change ratio of ~83%)
[52,53]. Furthermore, the use of the standalone ZnTe-based alloys is
impractical, given that they may be subject to a degree of particle
pulverization due to the volume expansion during the repeated lithia-
tion/delithiation processes, which results in a low rate capability and
severe capacity fading.
Hence, the application of an appropriate buffering matrix to the
active material may effectively enhance the electrochemical perfor-
mances. One of the most promising reinforcements that have been
verified in several recent studies is the TiC-C hybrid conductive matrix,
which has remarkable properties based on the good mechanical prop-
erties of TiC (high stiffness, electrochemical stability, and high con-
ductivity) and the synergetic buffering roles between TiC and C during
cycling [54,55]. Therefore, this hybrid matrix can act as a structural
barrier and prevent the aggregation of active particles as well as par-
ticle pulverization, which improves the electrochemical characteriza-
tions of various Li-alloying active materials [22,24,30,31,37].
We herein report an effective strategy to achieve good electro-
chemical performances by the introduction of intermetallic ZnTe na-
noparticles into the multifunctional TiC-C hybrid conductive matrix,
which results in the preparation of the ZnTe@TiC-C composite using
the primary annealing followed by the secondary ball-milling process.
The good electrochemical performance of the ZnTe@TiC-C electrode
based on the following advantages of this nanocomposite is demon-
strated: (i) the formation of intermetallic ZnTe contributes to the mi-
tigation of the change in volume via the progressive electrochemical
reactions during cycling, and enhances the conductivity; and (ii) the
presence of the TiC-C hybrid conductive matrix can suppress the vo-
lume expansion of active ZnTe and prevent the particle disruption
during repeated cycling. Furthermore, this efficient hybrid matrix can
provide enhanced electrical conductivity, which can shorten the Li+
ion diffusion distance and facilitate electron transport.
2. Experimental section
2.1. Material fabrication
The ZnTe-based nanocomposites were synthesized via annealing
followed by ball milling. In brief, powders of Zn (< 10 µm, ≥ 98%,
Aldrich), Te (200 mesh, 99.8%, Aldrich), and Ti (325 mesh, 99.99%,
Alfa Aesar) were used as raw-materials with four different molar ratios
(1:1:0.46, 1:1:1.07, 1:1:1.93, and 1:1:3.22). The primary annealing in
argon atmosphere was applied at 600 °C for 8 h at the heating rate of 5
°C min−1 for the mixed-powder of Zn-Te-Ti. Subsequently, the heat-
treated powder of Zn-Te-Ti and an appropriate amount of carbon black
(99.99%, Alfa Aesar) were added into a ZrO2 bowl (80 cm3) with
hardened ZrO2 balls in an Ar atmosphere, such that the compositions of
the TiC phase were estimated to be 10 wt%, 20 wt%, 30 wt%, and 40 wt
%, respectively, with 20 wt% of excess carbon black. The secondary
ball-milling was operated at a speed of 300 rpm for 40 h using a pla-
netary ball mill (Pulverisette 5, Fritch). The resulting products were
denoted as ZnTe@TiC(10%)-C, ZnTe@TiC(20%)-C, ZnTe@TiC(30%)-C,
and ZnTe@TiC(40%)-C. For comparison, ZnTe@C composites without
TiC was prepared by the same procedure without Ti at the initial mixing
stage. Another control sample of TiC was prepared by ball milling at a
molar ratio of 1:1 (Ti:C).
2
Applied Surface Science 534 (2020) 147679
2.2. Materials characterization
The crystal structure of the as-prepared samples was examined
using X-ray diffraction (XRD; D/MAX-2200 Rigaku, Japan), where 2θ
Bragg angles were scanned over a range of 20–80° at a scan speed of 2°
min−1. Scanning electron microscopy (SEM, Hitachi S4700, Japan) and
high-resolution transmission electron microscopy (HRTEM, JEOL JEM-
2100F) were used to characterize the morphology of as-prepared
powders. The compositions of the powders were analyzed using scan-
ning transmission electron microscopy (STEM), and the corresponding
energy-dispersive X-ray spectroscopy (EDS) mapping images were ob-
tained for each constituent element. The ex-situ XRD and ex-situ SEM
measurements were performed in which the powders was collected
from the electrode after a certain number of cycling.
2.3. Electrochemical measurements
The working electrodes were prepared using the following proce-
dures, to evaluate the electrochemical performances of the nano-
composites. The slurries, which included the active materials, carbon
black, and poly(vinylidene fluoride) (PVDF) with a weight ratio of
70:15:15 were mixed into N-methyl-pyrrolidone (NMP) as a solvent.
After casting those slurries on copper foils using a doctor blade, the
films were then dried at 70 °C overnight in a vacuum oven. The coin-
type cell (CR2032) include an as-prepared electrode as a working
electrode, a metallic lithium foil as a counter electrode, polyethylene
(PE) as a separator, and an electrolyte consisting of 1 M LiPF6 in
ethylene carbonate (EC)/diethylene carbonate (DEC) (1:1 by v/v).
Cyclic voltammetry (CV) was carried out using a ZIVE MP1 (WonAtech)
machine in the voltage range of 0.01–2.5 V at a scanning rate of
0.1 mV s−1. A battery cycler (WBCS3000, WonAtech) was operated in
the potential range of 0.01–2.5 V to test galvanostatic charge/discharge
measurements (at a constant current density of 100 mA g−1) and rate
capabilities (at different current densities of 0.1 A g−1, 0.5 A g−1, 1 A
g−1, 3 A g−1, 5 A g−1, and 10 A g−1). Thereafter, electrochemical
impedance spectroscopy (EIS) measurements were carried out within a
frequency range of 0.1–100,000 Hz at 10 mV AC amplitude using a
ZIVE MP1 (WonAtech) analyzer. To estimate the volumetric capacity,
the tap density of as-synthesized powder was measured using powder
density measurement equipment (MAT-7000, Seishin, Japan).
3. Results and discussions
Fig. 1 presents the schematic of the overall synthesis of the com-
posites using a facile annealing step followed by a ball-milling process.
In the initial annealing step, a metastable Zn-Te-Ti alloy was formed
including a new phase of ZnTe and three unreacted continents of Zn, Te,
and Ti, which are confirmed by XRD result in Fig. S1. In the subsequent
ball-milling step, with the presence of amorphous carbon, the TiC phase
was synthesized along with the complete formation of ZnTe phase from
unreacted continents of Zn and Te. The as-prepared composite includes
ZnTe, TiC, and amorphous carbon (denoted as ZnTe@TiC-C composite).
The chemical reaction for these two steps can be summarized as fol-
lows.
Annealing ball milling
Zn + Te + Ti ZnTe + Zn + Te + Ti ZnTe@TiC C
(1)
The XRD patterns (Fig. 2a) of ZnTe-based composites with various
estimated TiC content (0 wt%, 10 wt%, 20 wt%, 30 wt%, and 40 wt%)
confirm the successful formation of the cubic phase structure of ZnTe
(PDF#15–0746) in all samples. In detail, the peaks at 2θ = 25.3°, 29.2°,
41.8°, and 49.5° observed for all samples correspond to the (1 1 1),
(2 0 0), (2 2 0), and (3 1 1) planes of crystalline ZnTe with the interplanar
spacing of ~3.5 A°, ~3.1 A°, ~2.16 A°, and 1.84 A°, respectively. In
addition, the successful formation of the conductive TiC phase during
Q.H. Nguyen, et al. Applied Surface Science 534 (2020) 147679

Fig. 1. Schematic of overall synthesis of ZnTe@TiC-C composite.

SEM. As shown in Fig. 2c, the average particle sizes of the ZnTe@TiC-C
nanocomposite were generally in the range of sub-micrometers to
several micrometers. From a comparison with the ZnTe and ZnTe@C
composites, the ZnTe@TiC-C nanocomposite exhibited a greater
number of particles with sizes less than 100 nm (up to 86% in Fig. S4).
This can be attributed to the effect of the mechanically strong TiC
present in the ZnTe@TiC-C composite, in which the fragmentation of
ZnTe particles was more pronounced during the ball-milling process.
Furthermore, the TEM image (Fig. S5a) and the STEM images with the
corresponding elemental mapping (Fig. S5b) revealed the homogeneous
distribution of ZnTe, TiC, and C within the composite. These structural
features of ZnTe@TiC-C are considered as beneficial for anode mate-
rials in LIBs.
Fig. 3 presents a comparison between the first-cycle discharge/
charge profiles of ZnTe@C and those of various ZnTe@TiC-C elec-
trodes, as obtained from the galvanostatic charge and discharge (GCD)
measurements at a current density of 100 mA g−1, over a voltage range
of 0.01–2.5 V (vs. Li/Li+) (the detailed data are summarized in Table
Fig. 2. (a) XRD patterns of ZnTe-based composites; (b) HRTEM image (inset:
S2). As seen clearly, the initial discharge and charge capacities gen-
FFT pattern) and (c) SEM image of ZnTe@TiC-C composite.
erally decrease with the increase of TiC content from 0 wt% to 40 wt%,
given that the contribution of TiC to the capacity was lower (~125 mAh
ball milling in the presence of Ti and C was demonstrated by the ad- g−1 in Fig. S6) [56,57] than that of ZnTe. In detail, the initial dis-
ditional peaks at ~35.9°, 41.7°, 60.4°, and 76.1° corresponding to the charge/charge capacities of of ZnTe@-C, ZnTe@TiC(10%)-C,
(1 1 1), (2 0 0), (2 2 0), and (3 1 1) planes of crystalline TiC ZnTe@TiC(20%)-C, ZnTe@TiC(30%)-C, and ZnTe@TiC(40%)-C were
(PDF#32–1383), which was in good agreement with the findings of 926/634, 859/598, 667/446, 544/334, and 596/291 mAh g−1/mAh
previous studies [22,24,29–31]. With increasing TiC content, the TiC
peaks were more distinct (dotted marks at 2θ of ~35.9°), and the ZnTe
peaks reduced their intensities. This can be attributed to the increased
content of TiC, given that the sequential collision and deformation of
ZnTe against the mechanically hard and strong TiC phase reduced the
crystallinity of the ZnTe during the milling process [54,55]. Although a
portion of the pure Zn, Ti, and Te phases remained after the annealing
(dotted circles in Fig. S1), they were all primarily converted into the
well-defined ZnTe and TiC phases after the secondary ball-milling
process (Fig. 2a) except for a trace amount of pure Ti (1.1 wt% as
calculated from Table S1 with Fig. S2 and S3) in ZnTe@TiC(20%)-C.
From the Table S1, the actual contents of ZnTe/C in ZnTe@C and
ZnTe@TiC(20%)-C were 81%/19% and 60.6%/19.6%, respectively,
which were not much deviated from the theoretical contents (80%/20%
and 60%/20% of ZnTe/C in ZnTe@C and ZnTe@TiC(20%)-C, respec-
tively). From the HRTEM image (Fig. 2b), the presence of ZnTe and the
TiC nanocrystallite phases could be confirmed with interplanar dis-
tances of 0.216 nm (2 2 0) phase of ZnTe and 0.249 nm (1 1 1) phase of
TiC, which were in good agreement with the XRD results discussed
above. Also, the presence of crystalline ZnTe (2 2 0) and TiC (1 1 1)
could be confirmed from the corresponding FFT image by indexing the
lattice planes and interplanar spacings (inset in Fig. 2b). The powder
Fig. 3. Initial charge/discharge profiles of ZnTe@C and various ZnTe@TiC-C
morphology of the ZnTe@TiC-C nanocomposite was characterized by
electrodes at 100 mA g−1.

3
Q.H. Nguyen, et al.
Fig. 4. CV curves of (a) ZnTe-TiC(10%)-C; (b) Ex-situ XRD patterns of the ZnTe@TiC-C electrode at three different cut-off potentials and (c) Schematic illustration for
the reaction mechanism.
g−1, corresponding to their initial coulombic efficiencies (ICEs) of
~68%, 67%, 67%, 64%, 51%, respectively. The ICEs exhibited a similar
trend to the initial discharge/charge capacities, in that the increase in
the TiC content led to a decrease in the ICEs. This could be attributed to
the lower crystallinity of ZnTe with a higher TiC content, which pre-
vents Li+ ion diffusion during the initial cycling process and induces
more side reactions, thus resulting in the formation of an SEI layer over
a wide range of potential [24]. As a result, distinct plateaus associated
with SEI layer formation at ~0.7 V were observed for the
ZnTe@TiC(30%)-C and ZnTe@TiC(40%)-C electrodes, which were re-
latively unclear for the lower TiC content cases (ZnTe@C,
ZnTe@TiC(10%)-C, and ZnTe@TiC(20%)-C electrodes).
To better understand the electrochemical reaction mechanism, CVs
(Fig. 4a and Fig. S7) and ex-situ XRD measurements (Fig. 4b) were
carried out on the ZnTe@TiC-C composites. First, CV plots in all cases of
ZnTe@TiC-C electrodes exhibit similar behaviors, in which all the peak
positions were consistent with the voltage plateaus observed in GCD
voltage profiles (Fig. 3). However, in comparison with the cases of TiC
contents of 10% and 20%, the ZnTe-based electrodes with 30% and
40% of TiC content showed generally broader voltage ranges, which
could be caused by the reduced crystallinity of ZnTe when the TiC
content was high. In the initial lithiation process, a reduction peak
observed at ~1.7 V in all cases of ZnTe-based electrodes related to the
formation of Li2Te and Zn phase from the alloying reaction between Te
and Li+ ions (ZnTe + 2Li+ → Li2Te + Zn at 1.7 V). Two reduction
peaks at 0.9 and 0.7 V indicate the formation of Li2Te and LixZn from
ZnTe (ZnTe + (2 + x)Li+→ Li2Te + LixZn at 0.9 and 0.7 V). In ad-
dition, the various small peaks observed in the voltage range of
0.4–0.01 V are associated with the successive formation of a LiZn phase
from the reaction between Zn and Li-ions (LixZn + (1-x)Li+ → LiZn at
0.4–0.01 V) along with a solid-electrolyte interphase (SEI) layer for-
mation on the surface of the electrode material [37,43]. In the initial
delithiation process, the sequential reversible reaction of LiZn to Zn
occurred when the potential increased from 0.01 V to 1.25 V (LiZn →
LixZn → xLi+ + Zn at 1.25 V). Meanwhile, an oxidation peak observed
at ~2.0 V represents the dealloying reaction of Li2Te phase
(Li2Te + Zn → ZnTe + 2Li+ at 2.0 V) [43]. Moreover, the reduction
peak at ~0.9 V was shifted toward a higher potential after the first
4
Applied Surface Science 534 (2020) 147679
cycle, due to the reduced electrode polarization during the discharge
processes, whereas all the oxidation peaks were remained at the same
potentials [24]. Secondly, the alloying/dealloying reaction mechanism
for ZnTe@TiC-C during cycling was further confirmed by carrying out
ex-situ XRD analysis on the ZnTe@TiC-C electrode based on three cut-
off potentials as (Fig. 4b) indicated using arrows in the CV plots
(Fig. 4a). In the pristine state, all the observed ZnTe peaks were con-
sistent with the XRD results (Fig. 2a). When the electrode was dis-
charged to 0.01 V vs. Li/Li+ (full discharge state), the additional peaks
of Li2Te (~23°, ~27°, and ~39°) were detected, and the ZnTe peaks
disappeared, which indicates the complete conversion reaction of ZnTe.
We note the peaks corresponding to LiZn were not clearly detected after
full discharge. After charging to 2.5 V (fully charge state), the phases of
Li2Te and LiZn were not observed, whereas crystalline ZnTe peaks re-
appeared, indicating the reversible lithiation/delithiation process
without structural changes. In addition, the peaks from TiC were not
clearly detected due to the low signal level in the ex-situ XRD mea-
surements [43]. To further investigate the reaction mechanism, the ex-
situ HRTEM was performed after full discharge and charge (Fig. S8); the
results showed the lattice spacings of 0.376 nm and 0.326 nm which
correspond to the (1 1 1) and (2 0 0) planes of Li2Te and the lattice
distances of 0.220 nm and 0.188 nm which indicate the (2 2 0) and
(3 1 1) planes of LiZn, respectively, after full discharge (Fig. S8a).
Meanwhile, at fully charged state (Fig. S8b), the crystalline phases of
ZnTe (0.352 nm d-spacing from (1 1 1) plane) and TiC (0.216 nm d-
spacing from (2 0 0) plane) were observed, indicating the reversible
reaction of ZnTe. Based on the CV results and ex-situ XRD patterns, the
detailed electrochemical mechanism of the ZnTe@TiC-C electrode
during the first lithiation/delithiation can be schematically illustrated
as Fig. 4c and expressed as follows:
During the lithiation process:
ZnTe → Li2Te + Zn → Li2Te + LixZn → Li2Te + LiZn (2)
During the de-lithiation process:
Li2Te + LiZn → Li2Te + LixZn → Li2Te + Zn (3)
→ ZnTe
Fig. 5a presents a comparison of the cyclic performances and
Q.H. Nguyen, et al.
coulombic efficiencies between ZnTe@TiC-C (20 wt% TiC) and
ZnTe@C (0 wt% TiC) electrodes at a current density of 100 mA g−1. In
comparison with ZnTe@TiC-C, the ZnTe@C electrode exhibited a
higher initial discharge capacity (926 mAh g−1 as compared to 667
mAh g−1), as it contained higher ZnTe active material content (80 wt%
as compared to 60 wt%) in the composite. However, there was a rapid
decrease in the capacity during the 150 cycles (~298 mAh g−1 with a
corresponding capacity retention of 55%). Meanwhile, the introduction
of the TiC-C buffering matrix into the ZnTe alloy resulted in a sig-
nificant improvement in the cyclic stability, which exhibited a capacity
of ~547 mAh g−1 after 300 cycles (capacity retention of 108% relative
to the capacity at 2nd cycle). The gradually increasing capacity with the
increasin in cycle number may be attributed to the gradual activation of
the electrode and polymer/gel-like film formation [58–60]. Further-
more, the optimum TiC content in the ZnTe@TiC-C composites was
evaluated based on the comparison of the cyclic performances, as
shown in Fig. S9a. Among these electrodes, the ZnTe-TiC(10%)-C ex-
hibited the highest capacity after 100 cycles (535 mAh g−1 as com-
pared to ~524, 330, and 330 mAh g−1 for ZnTe@TiC(20%)-C,
ZnTe@TiC(30%)-C and ZnTe@TiC(40%)-C, respectively). However, the
ZnTe-TiC(10%)-C showed the instable cycling behavior after 100 cycles
where the capacity decreased to ~328 mAh g−1 after 300 cycles. This
could be attributed to the insufficient amount of TiC in the composite
that could not sufficiently prevent the ZnTe active particles from the
volume expansion during repeated cycling. Although the ZnTe-based
electrodes with 30 wt% and 40 wt% of TiC content exhibited much
improved cyclic stabilities, they showed relatively low reversible dis-
charge capacities due to their low ZnTe contents (~351 and 357 mAh
g−1 for ZnTe@TiC(30%)-C and ZnTe@TiC(40%)-C, respectively).
When the TiC content was optimized to be 20 wt% (ZnTe@TiC(20%)-
C), both high capacity and cyclic stability were realized. In particular, it
exhibited a capacity of ~547 mAh g−1 after 300 cycles (capacity re-
tention of 82%), which can be attributed to the introduction of an ap-
propriate amount of TiC to the TiC-C hybrid matrix, which effectively
suppresses the aggregation of active ZnTe and mitigates the stresses and
strains in the ZnTe during the extended cycling. In addition, the long-
term cyclic performance of the ZnTe@TiC(20%)-C electrode measured
5
Applied Surface Science 534 (2020) 147679
Fig. 5. (a) Cyclic performances (gravi-
metric capacity) of ZnTe@C and
ZnTe@TiC-C electrodes at 100 mA g−1;
(b) Long-term cyclic performance
(gravimetric and volumetric capacity)
of ZnTe@TiC-C electrodes at 1 A g−1;
(c) Rate capability of ZnTe@C and
ZnTe@TiC-C electrodes; (d) Normalized
capacity retention of ZnTe@C and
ZnTe@TiC-C electrodes at different
current densities.
at a high current density of 1 A g−1 (Fig. 5b) demonstrates the stable
specific capacity of ~480 mAh g−1 after 500 cycles, corresponding to
the capacity retention of 106% (relative to the capacity at 2nd cycle).
The result also showed the very high volumetric capacity of ~700 mAh
cm−3 after 500 cycles, which was converted from the specific capacity
with the measured tap density (1.46 g cm−3). It is of note that the
volumetric capacity can be calculated by multiplying the measured
specific capacity by the tap density. This value (~700 mAh cm−3) is
greater than the theoretical volumetric capacity of the commercial
graphite anode (~385 mAh cm−3 with low tap density of 0.96 g cm−3)
by a factor of 1.8 [28,30], which confirms that the ZnTe@TiC-C is
applicable to practical energy storage systems.
To further evaluate the effect of the TiC-C matrix on the composites,
the rate capabilities (Fig. 5c) and the normalized capacity retentions
(Fig. 5d) of the ZnTe@C and ZnTe@TiC-C electrodes were evaluated at
current densities ranging from 0.1 to 10 A g−1. As shown in Fig. 5c, the
ZnTe@TiC-C electrode retained a high specific capacity of ~432 mAh
g−1 at a very high current density of 10 A g−1, which corresponded to a
capacity retention of ~84% compared to the capacity at 0.1 A g−1;
whereas the ZnTe@C electrode exhibited capacities within the ap-
proximate range of ~325 mAh g−1 at 10 A g−1, corresponding to
~67% of capacity retention. Moreover, when the current density was
returned from 10 A g−1 to its initial value of 0.1 A g−1, the capacity
retention of the ZnTe@TiC-C electrode was slightly higher (~545 mAh
g−1) than the initial capacity (514 mAh g−1), which indicates an in-
creased activation of the electrode. This better performance can be at-
tributed to the facile Li+ ion transport property of the active particles,
in addition to the uniform incorporation of the conductive TiC-C dis-
persing matrix that confers the high conductivity for the composites
[22,24,30,31,37]. The normalized capacity retentions, as shown in
Fig. 5d, further confirm the relatively higher capacity retention of
ZnTe@TiC-C electrode than that of the ZnTe@C electrode. Further-
more, the comparison of rate capability between various TiC content in
ZnTe@TiC-C electrode was presented in Fig. S9b, which demonstrated
the best performance of the ZnTe@TiC(20%)-C as compared to the
others.
Finally, EIS measurements (Fig. 6a and Table S3) and ex-situ SEM
Q.H. Nguyen, et al.
Fig. 6. (a) EIS spectra of ZnTe@C and ZnTe@TiC-C electrodes after 50 cycles; Ex-situ SEM images of (b) ZnTe@C and (c) ZnTe@TiC(20%)-C electrodes after 50
cycles.
(Fig. 6b and c) imaging were conducted after 50 cycles of cyclic per-
formance at 100 mA g−1 to evaluate the changes in the conductivities
and morphology of ZnTe@TiC-C and ZnTe@C electrodes during cy-
cling. As a result, the ZnTe@TiC-C electrode exhibited relatively lower
charge-transfer resistances (smaller semi-circles) when compared with
that of the ZnTe@C electrode after 50 cycles. Also, the cross-sectional
image of ZnTe-C (Fig. 6b) revealed a poor morphology with distinct
cracks, pulverization, and aggregation; whereas the ZnTe@TiC-C elec-
trode retained its original morphology with a smooth surface, and no
cracks or peeling were observed (Fig. 6c). These results confirm that the
addition of an appropriate amount of TiC to the TiC-C hybrid matrix
allows for the development of good electron transport pathways be-
tween active ZnTe particles, thereby suppressing the electrode pulver-
ization and enhancing the electronic conductivity of the composites,
which further verify the effectiveness of the addition of the TiC-C ma-
trix into ZnTe for the enhancement of the electrochemical performance.
4. Conclusion
In summary, ZnTe@TiC-C nanocomposites with various TiC con-
tents were successfully synthesized using a facile two-step procedure of
the primary annealing followed by the secondary ball milling. The as-
prepared ZnTe@TiC-C nanocomposite includes the ZnTe nanocrys-
tallites uniformly distributed in the well-mixed TiC-C hybrid conductive
matrix, which resulted in the superior electrochemical performance
with respect to the reversible capacity, life-span, and high rate cap-
ability. Among the various ZnTe-based electrodes, the ZnTe-TiC(20%)-
C electrode demonstrated the best performance, exhibiting a reversible
capacity of 547 mAh g−1 at 100 mA g−1 after 300 cycles, and an good
rate capability with a capacity retention of 84% at 10 A g−1. Moreover,
the ZnTe-TiC(20%)-C exhibited a stable reversible capacity of ~480
mAh g−1 until 500 cycles at a high current density of 1 A g−1, which
corresponds to the volumetric capacity of ~700 mAh cm−3. These good
characteristics of the ZnTe@TiC-C nanocomposite confirm its high
6
Applied Surface Science 534 (2020) 147679
potential as a promising high-performance anode material for re-
chargeable Li-ion storage.
CRediT authorship contribution statement
Quoc Hai Nguyen: Data curation, Writing - original draft,
Investigation. Quoc Hanh Nguyen: Data curation, Writing - original
draft, Investigation. Seongjoon So: Data curation, Investigation.
Jaehyun Hur: Conceptualization, Methodology, Writing - review &
editing, Supervision, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by the Korea Institute of Energy
Technology Evaluation and Planning (KETEP) and the Ministry of
Trade, Industry & Energy (MOTIE) of the Republic of Korea (No.
20194030202290) and by the Basic Science Research Program through
the National Research Foundation of Korea (NRF) funded by the
Ministry of Education (NRF-2019R1F1A1057709).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2020.147679.
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