Applied Surface Science 509 (2020) 144718

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Applied Surface Science

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Full Length Article

High-performance ZnTe-TiO2-C nanocomposite with half-cell and full-cell T

applications as promising anode material for Li-Ion batteries
⁎
Quoc Hanh Nguyena,1, Quoc Hai Nguyenb,1, Jaehyun Hura,
a
Department of Chemical and Biological Engineering, Gachon University, Seongnam, Gyeonggi 461-701, Republic of Korea
b
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City 700000, Viet Nam

A R T I C LE I N FO A B S T R A C T

Keywords: C-coated ZnTe-TiO2 nanocomposite is successfully synthesized via annealing followed by high-energy me-
Zinc telluride chanical milling. ZnTe-TiO2-C nanocomposite is comprised of intermetallic ZnTe nanoalloy homogeneously
Titanium oxide distributed in a hybrid matrix of rutile TiO2 and conductive amorphous C. The presence of rutie TiO2 and C
Anode significantly improves the electrochemical performance of ZnTe; that is, highly stable cyclic performance
High-energy mechanical milling
(611 mAh g−1 at 0.1 A g−1 with ~95% capacity retention over 300 cycles and 492 mAh g−1 at 0.5 A g−1 after
Li-ion batteries
500 cycles) and good rate capability (76% capacity retention at 10 A g−1 compared with the capacity at
0.1 A g−1). The improved electrochemical performance is primarily associated with the TiO2-C hybrid matrix
that efficiently surrounds the ZnTe nanocrystallites, thereby providing high electric conductivity and at the same
time functioning as a buffering medium that alleviates the large volume change during extended cycling.
Furthemore, the practical application of ZnTe-TiO2-C as an anode is investigated with full cell consisting of a
ZnTe-TiO2-C anode and a LiFePO4-graphite (LFP@G) cathode. The ZnTe-TiO2-C//LFP@G full cell exhibits good
cyclic stability with 79% capacity retention at 0.1 A g−1 after 200 cycles. These results suggest the ZnTe-TiO2-C
nanocomposite is a promising candidate for a high-performance anode in next-generation LIBs.

1. Introduction anode material because it is naturally abundant, eco-friendly and in-

Recently, the rapid advances in portable electronics and electric
vehicles have necessitated the development of next-generation energy
storage devices with high energy densities and enhanced safety. In this
regard, Li-ion batteries (LIBs) are one of the most promising recharge-
able battery systems because of their high energy and power densities,
long cycle lives, and excellent rate capabilities [1–4]. Despite the low
cost and good cyclic stability of commercial graphite, it has a limited
energy density owing to its relatively low theoretical gravime-
triccapacity of 372 mAh g−1, low volumetric capacity resulting from
low tap density (< 1 g cm−3), and poor rate capability, as well as the
safety issues (Li plating on graphite surfaces). Thus, enormous attempts
have been implemented to develop alternative anode materials to re-
place graphite anodes [5–10].
In recent years, Li-alloying materials have been proposed as new
high-performance LIB anodes because of their high theoretical capa-
cities resulting from a large number of Li+ ions during cycling and their
high reaction potentials, which mitigate safety issue associated with Li
plating [11–21]. Zn has been extensively investigated as a potential
expensive. Additionally, Zn possesses such advantages as an extremely
high volumetric capacity (2927 mAh cm−3) and a moderate working
potential (~0.4 V vs. Li/Li+). However, the practical application of Zn
alone still causes the huge volume expansions and the pulverization of
active particles during Li alloying/dealloying, resulting in poor elec-
trochemical performance, as with other Li-alloying materials [22–27].
One of the effective approaches for resolving this problem is the in-
troduction of appropriate mechanical buffer to the active composites,
which can efficiently absorb the strain generated from cycling and al-
leviate particle agglomeration. Titanium oxides have been considered
as supplemental materials for preventing the pulverization of the alloy
anode in LIBs owing to their structural stability [28–32]. Furthermore,
rutile TiO2 can react with Li reversibly as an active material [33–39].
The lithiation/delithiation reaction of TiO2 can be summarized as fol-
lows.
TiO2 + xLi+ + xe− ↔ Lix TiO2 (0 ≤ x ≤ 1) (1)
In addition, conductive C coating has been regarded as a strategy to
improve the electrochemical performance of LIBs.

⁎
Corresponding author.
E-mail address: 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.2019.144718
Received 19 September 2019; Received in revised form 11 November 2019; Accepted 15 November 2019
Available online 28 November 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
Q.H. Nguyen, et al.
Another strategy to prevent the high volume expansion of Zn during
cycling is the combination of zinc with other metallic components.
Telluride is a great candidate in alloying with Zn because it can react
with Li+ to form Li2Te (~1.9 V), with a reaction potential far from that
of Zn (~0.4 V), implying that progressive electrochemical reactions
occur during cycling [14,19]. Therefore, the incorporation of Te into
Zn, forming intermetallic ZnTe, can be an effective strategy for alle-
viating the abrupt volume expansion upon prolonged cycling. Fur-
thermore, it has an extremely high theoretical volumetric capacity of
~2621 mAh cm−3 and a higher electric conductivity (2 × 10-
4
MS m−1) than other elements in the chalcogen group (Se, 1 × 10-
10
MS m−1; S, 5 × 10-22 MS m−1) which can enhance the electro-
chemical performance of Zn-based anode in LIBs.
In this study, we synthesize a ZnTe-TiO2-C composite via a combi-
nation of annealing and high-energy mechanical milling (HEMM). The
bimetallic ZnTe alloy nanocrystallites were embedded in a conductive
hybrid matrix of TiO2 and C, which yielded excellent electrochemical
performance (reversible and stable cycle life and good rate capability).
The merits of ZnTe-TiO2-C nanocomposite as a high-performance anode
are regarded as follows: (i) the distinct reaction potentials between zinc
and telluride with Li+ allows the sequential electrochemical lithiation/
delithiation and reduces the abrupt volume expansion upon cycling; (ii)
the introduction of Te and the conductive C for Zn improves the electric
conductivity; and (iii) the conductive TiO2-C hybrid matrix acts as a
buffering medium that suppresses the huge volume expansion of active
ZnTe and prevents particle agglomeration during cycling.
2. Experimental section
2.1. Material preparation
To prepare the ZnTe-TiO2-C nanocomposite, ZnO powder
(< 50 nm, > 97%, Sigma–Aldrich), Te powder (200 mesh, 99.8%,
Sigma-Aldrich), and Ti powder (325 mesh, 99.99%, Alfa Aesar) were
mixed in a mortar with a molar ratio of 2:2:1. Then, the resulting
mixtures were annealed under a flowing Ar atmosphere at 600 °C for
8 h. Subsequently, acetylene carbon black powder was added in such a
way that the mass ratio of carbon black was 30 wt% of the total weight
to the annealed ZnO-Te-Ti alloy powder with and manually ground.
These powder mixtures were then transferred in a ZrO2 bowl (80 cm3)
in which two different sized hardened ZrO2 balls (diameters of 3/8 and
3/16 in.) were placed along with powder at the mass ratio of 1:20
(powder:balls). The bowl was tightly sealed under an Ar atmosphere in
a glove box, and HEMM was operated at 300 rpm for 20 h utilizing a
planetary mechanical milling machine (Pulverisette 5, Fritch). For
comparison, a ZnTe-TiO2 sample was separately synthesized via the
same procedure without the addition of carbon black at the milling
step. Another control sample (ZnTe-C) was synthesized using Zn, Te,
and C powders, with a weight ratio of 7:3 (ZnTe:C). The overall syn-
thetic procedure for producing the ZnTe-TiO2-C composite is illustrated
in Fig. 1. During the first annealing step, the powder mixtures of ZnO,
Te, and Ti were mostly converted into the ZnTe alloy and the TiO2
phase, along with the metastable ZnO-Te-Ti alloy. In the second HEMM
process with C addition, the formation of the ZnTe-TiO2-C
Fig. 1. Overall synthesis process for the ZnTe-TiO2-C composite.
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Applied Surface Science 509 (2020) 144718
nanocomposite from the metastable ZnO-Te-Ti alloy was completed,
without impurities. The overall chemical reaction is expressed as fol-
lows.
Annealing
ZnO + Te + Ti → ZnTe + TiO2 + metastable ZnO − Te − Ti
HEMM
(+C )
→ ZnTe − TiO2 − C (2)
2.2. Material characterization
The crystalline structures of the as-synthesized powders were
characterized using an X-ray diffraction (XRD; D/MAX-2200 Rigaku,
Japan) with Cu Kα radiation (λ = 1.5406 nm) (scan rate: 2° min−1, 2θ
range: 20°–80°). To understand the reaction mechanism of ZnTe-TiO2-C
anode, ex -situ XRD analysis was performed for ZnTe-TiO2-C electrodes
at pristine, fully-discharged, and fully charged states. X-ray photoelec-
tron spectroscopy (XPS, Kratos AXIS Nova) was performed to in-
vestigate the chemical and bonding states of the composite. The mi-
croscopic morphologies of the as-prepared powder samples were
analyzed using scanning electron microscopy (SEM, Hitachi S4700,
Japan) and high-resolution transmission electron microscopy (HRTEM,
JEOL JEM-2100F) analyses. The elemental compositions of the as-
synthesized samples were analyzed using scanning transmission elec-
tron microscopy (STEM) equipped with energy-dispersive X-ray spec-
troscopy (EDS). Ex-situ SEM analysis was conducted to examine the
different morphologies of the electrode materials for the disassembled
cell after cycling.
2.3. Electrochemical measurements
CR2032 coin cells were assembled in a glove box using an anode as
a working electrode, a metallic Li foil as a counter electrode, 1 M LiPF6
solution dissolved in ethylene carbonate/diethylene carbonate (EC/
DEC, 1:1, v:v) as an electrolyte, and polyethylene (PE) as a separator.
The working electrodes were prepared by mixing the as-prepared
powders (70 wt%), conductive Super P carbon black (15 wt%), and a
binder (15 wt% polyvinylidene fluoride (PVDF)) in an N-methyl-pyr-
rolidone (NMP) solvent. These slurry mixtures were then coated onto
Cu foils via the doctor-blade technique and vacuum-dried overnight at
70 °C. The electrochemical performance was measured within the vol-
tage range of 0.01–2.5 V vs. Li/Li+ galvanostatically at a current
density of 0.1 A g−1 with a WBCS3000 battery cycler (WonATech).
Cyclic voltammetry (CV) was carried out at a scan rate of 0.2 mV s−1
using a ZIVE MP1 (WonATech) machine. The measurement of rate
capability was performed at a current density range of 0.1–10 10 A g−1.
Electrochemical impedance spectroscopy (EIS) was measured in the
frequency range of 100 kHz–100 mHz using a ZIVE MP1 analyzer
(WonATech). For full-cell electrochemical measurements, LiFePO4-
graphite (LFP@G) electrode was synthesized as a cathode material
using one-step HEMM; The powders of LiFePO4 (< 5 µm, > 97%,
Sigma-Aldrich) and graphite (200 mesh, 99.9999%, Alfa Aesar) were
first mixed and manually ground at a mass ratio of 7:3. Subsequently,
the HEMM was applied for the mixture under an Ar atmosphere for 10 h
Q.H. Nguyen, et al.
Fig. 2. XRD patterns of the ZnTe-C, ZnTe-TiO2, and ZnTe-TiO2-C composites.
at 300 rpm. A coin-type (CR2032) full cells were prepared using ZnTe-
TiO2-C electrode (anode) and LFP@G electrode (cathode). PE was used
as the separator while the electrolyte was identical to that in half-cell.
The slurry for the cathode material was prepared by mixing 80 wt% of
LFP@G, 10 wt% of Super P, and 10 wt% of binder (PVDF dissolved in
Fig. 3. XPS spectra of the ZnTe-TiO2-C composite.
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Applied Surface Science 509 (2020) 144718
the NMP solvent). To enhance the stability of the full cell, the cells were
first pre-charged for cathode and pre-discharged for anode to stabilize
the solid–electrolyte interphase (SEI) layer. GCD cycling measurements
were performed with a WBC3000 battery cycler at 0.1 A g−1 in the
potential range of 1.0–3.8 V. The specific capacity of full cell was de-
termined based on the weight including both active anode and cathode
material, with their weight ratio of ~1:2 (anode:cathode).
3. Results and discussions
3.1. Characterization of synthesized samples
The XRD patterns of the ZnTe-TiO2-C, ZnTe-TiO2, and ZnTe-C
composites are shown in Fig. 2. The XRD patterns of all these samples
exhibited the peaks of crystalline ZnTe, which well match the reference
peaks (PDF#15-0746), suggesting the successful formation of the ZnTe
phase. For the ZnTe-TiO2-C and ZnTe-TiO2 nanocomposites, additional
peaks corresponding to the crystalline structure of rutile TiO2 (PDF#21-
1276) were observed at ~27.6°, 36.1°, 54.3°, and 76.5°, which are as-
signed to the (1 1 0), (1 0 1), (2 1 1), and (2 0 2) planes, respectively.
Although small peaks corresponding to ZnO, Ti, and Te phases were
observed after the first heat treatment (Fig. S1), these phases were
completely transformed into ZnTe and TiO2 phases after the HEMM
(Fig. 2). In all cases, no other peaks were detected, suggesting that there
are no impurities formed during the milling process. The Raman spectra
shown in Fig. S2 verify the presence of C in the ZnTe-TiO2-C and ZnTe-C
composites. The first peak at ~1329 cm−1 is related to the Dl.-band of
the disordered C, and another peak at ~1584 cm−1 corresponds to the
G-band of the graphitized C [40]. For ZnTe-TiO2-C and ZnTe-TiO2, the
characteristic peaks of rutile TiO2 were observed at ~144, 445, and
610 cm−1, which are designated to the peaks of B1g, Eg, and A1g, re-
spectively. Additionally, the broad peak at ~235 cm−1 is ascribed to
the second-order or disorder-induced scattering [41].
XPS measurement was performed to investigate the chemical
bonding state and elemental composition of the ZnTe-TiO2-C nano-
composite (Fig. 3). In the Zn 2p spectrum, Zn 2p1/2 and Zn 2p3/2 peaks
were observed at ~1044.8 and 1021.7 eV, respectively (Fig. 3a). The
Q.H. Nguyen, et al.
Fig. 4. (a) SEM image, (b, c) HRTEM images, and (d) STEM image with EDS mapping images of the ZnTe-TiO2-C composite.
XPS peaks at ~583.9 and 573.1 eV in Fig. 3b are attributed to Te 3d5/2
and Te 3d3/2, respectively, confirming the reduction of ZnO to metallic
Zn and the successful formation of the ZnTe alloy after the HEMM [42].
The XPS peaks at ~464.4 and 457.9 eV can be indexed to Ti 2p1/2 and
Ti 2p3/2, respectively (Fig. 3c), and the O 1s peak at ~532.1 eV is as-
cribed to the O 1s electron binding energy for TiO2 (Fig. 3d) [43]. In the
C 1s spectrum, the peaks at ~288.9, 285.4, and 284.4 eV, corre-
sponding to the bonds of C]O, CeO, and CeC, respectively (Fig. 3e),
which can be explained by the partial transformation of the CeC bonds
in the amorphous C after the HEMM [44]. The full XPS spectra in Fig. 3f
confirm the presence of all the elements (Zn, Te, Ti, O, and C) in the
ZnTe-TiO2-C composite, indicating the successful formation of ZnTe,
TiO2, and C after the HEMM.
The microscopic morphology of the ZnTe-TiO2-C nanocomposite
were characterized via SEM, HRTEM, and elemental distribution
through STEM together with the EDS mapping. Fig. 4a and S3 show
SEM images of the ZnTe-TiO2-C, ZnTe-TiO2, and ZnTe-C composites. On
average, the particle sizes of as-prepared samples were in the range of
hundreds of nanometers –a few micrometers that are much smaller than
pristine powder sizes (owing to the continuous collision and fracture
during the HEMM. The HRTEM images presented in Fig. 4b and c in-
dicate the presence of nanosized ZnTe and TiO2 crystallites (darker
areas with sizes of 5–10 nm) dispersed into a carbon matrix without
aggregation. The interplanar distance of 0.352 nm is assigned to the
(1 1 1) plane of ZnTe, and the two interplanar spacings of 0.248 and
0.324 nm can be indexed to the (1 0 1) and (1 1 0) planes, respectively,
of the TiO2 phase. These results agree well with the foregoing XRD
analysis. The selected-area electron diffraction (SAED) patterns (insets
in Fig. 4b and c) confirm the presence of crystalline ZnTe (1 1 1) and
TiO2 ((1 0 1) and (1 1 0)), according to the interplanar spacings and
lattice planes. EDS mapping images in Fig. 4d reveal the uniform dis-
persion of ZnTe and TiO2 within the C matrix in the composite. Clearly,
the overlapped signal from Zn and Te as well as that from Ti and O
further confirms the successful formation of the ZnTe alloy and TiO2
phase. All these structural characterizations evidence that the ZnTe-
TiO2-C is composed of ZnTe and TiO2 nanocrystals well-distributed in a
conductive C matrix which provides a strong buffering effect by sup-
pressing the large stress from ZnTe crystallites, and increase the con-
ductivity of the composite.
3.2. Electrochemical performance of ZnTe-TiO2-C half-cell
Fig. 5a presents the charge/discharge voltage profiles for the 1st,
2nd, 10th, and 100th cycles of the ZnTe-TiO2-C nanocomposite elec-
trode from the GCD measurement at 0.1 A g−1 within the potential
range of 0.01–2.5 V. The ZnTe-TiO2-C electrode showed the initial
4
Applied Surface Science 509 (2020) 144718
discharge and charge specific capacities of 839 and 558 mAh g−1, re-
spectively, with the corresponding initial coulombic efficiency (CE) of
~66.5%. It is thought that the irreversible capacity loss can be ascribed
to the electrolyte decomposition and the SEI layer formation in the first
lithiation process. However, the ZnTe-TiO2-C electrode, after the first
cycle, exhibited excellent capacity retention, with a gradual increase in
the CE (94.8%, 98.1%, and 99.11% for the 2nd, 10th, and 100th cycles,
respectively). To investigate the Li-ion storage mechanism, CV was
measured on the ZnTe-TiO2-C nanocomposite for the initial three cycles
from 0.01 V to 2.5 V at a scanning rate of 0.1 mV s−1 (Fig. 5b). During
the initial discharge process, the first reduction peak at ~1.1 V was
detected, indicating the alloying reaction of rutile TiO2 to form the
Li0.5TiO2 phase, and the broad peak at ~0.9 V is assigned to the li-
thiation reaction of Te, forming the Li2Te phase [45,46]. The next two
peaks at ~0.6 and < 0.4 V can be ascribed to the formation of the SEI
film on the surface of the electrode and the progressive lithiations of Zn
that sequentially form various phases of Li-Zn (Zn → LiZn 4→LiZn) ,
respectively [20,22]. Upon the first charging cycle, a series of small
peaks were observed below 0.7 V, which are ascribed to the series of
delithiation reactions from LiZn to metallic Zn
(LiZn → Li2 Zn3 → LiZn2 → LiZn 4→Zn) [7,20]. The subsequent oxida-
tion peak detected at ~1.25 V corresponds to the transformation of
Li2Te into the ZnTe phase, and the broad peak at ~2.2 V is associated
with the delithiation reaction of Li0.5TiO2, which formed the TiO2 phase
[45,46]. In the subsequent cycles, while the SEI peaks at ~0.6 V dis-
appeared, all the lithiation/delithiation peaks in the 2nd and 3rd cycles
remained nearly unchanged, suggesting the good reversibility of the
ZnTe-TiO2-C electrode. The overall electrochemical reaction me-
chanism of the ZnTe-TiO2-C electrode can be written as follows.
During the discharge process:
TiO2 + 0.5Li+ + 0.5e− → Li 0.5TiO2 ( 1.1 V vs. Li/Li + ) (3)
ZnTe + 2Li+ + 2e− → Zn + Li2 Te ( 0.9 V vs. Li/Li + ) (4)
Zn → LiZn 4 → LiZn ( < 0.4 V vs. Li/Li + ) (5)
During the charge process:
LiZn → Li2 Zn3 → LiZn2 → LiZn 4 → Zn ( < 0.7 V vs. Li/Li + ) (6)
Zn + Li2 Te → ZnTe + 2Li+ + 2e− ( 1.25 V vs. Li/Li + ) (7)
Li 0.5TiO2 → TiO2 + 0.5Li+ + 0.5e− ( 2.2 V vs. Li/Li + ) (8)
To clarify the alloying/dealloying reaction mechanisms of the ZnTe-
TiO2-C electrode, ex-situ XRD experiments were carried out, as shown in
Fig. 5c. The electrochemical cells were disassembled at three potential
points, as marked by the arrows in Fig. 5b, corresponding to the as-
prepared, completely discharged, and completely charged states. For
Q.H. Nguyen, et al.
Fig. 5. (a) Voltage profiles; (b) CV curves; (c) ex situ XRD pattern of the ZnTe-TiO2-C electrode for the first cycle; (d) schematic illustration of the lithiation/
delithiation reaction mechanism.
the pristine electrode, the crystalline phases of ZnTe and TiO2, along
with a prominent peak corresponding to Cu foil, were observed, which
agrees well with the XRD results in Fig. 2. At fully discharged state
(0.01 V), several new peaks corresponding to Li0.5TiO2 (at ~24°, 26°,
37°, and 44°), Li2Te (at ~23°, 27°, 39°, and 46°) and LiZn (at ~41° and
48°) were observed, while the peaks corresponding to ZnTe and TiO2
disappeared, indicating the complete conversion of ZnTe and TiO2. At
completely charged state (2.5 V), all the peaks corresponding to LiZn,
Li2Te, and Li0.5TiO2 vanished, and new ZnTe and TiO2 peaks were
observed, indicating the complete reversibility of the active ZnTe and
TiO2 without structural changes upon the extended cycling process. The
detailed electrochemical mechanism is schematically presented in
Fig. 5d.
Fig. 6a compares the cyclic performance of the ZnTe-TiO2-C, ZnTe-
TiO2, and ZnTe-C electrodes at 0.1 A g−1 current density, and Fig. 6b
illustrates the long-term cyclic performance of these electrodes mea-
sured at a high current density (0.5 A g−1). As shown in Fig. 6a, among
the electrodes, ZnTe-TiO2 exhibited the lowest specific capacity of
~123 mAh g−1 after 300 cycles, which can be attributed to the large
volume changes of the active particles during the lithiation/delithiation
processes, which resulted in the particles pulverization and the loss of
electrical contact between the current collector and the active particles
upon extended cycling. The ZnTe-C electrode exhibited a significantly
higher capacity than ZnTe-TiO2 in the early stage of cycling
(472 mAh g−1 until 70 cycles). This can be interpreted by the effect of
the C-matrix addition to the ZnTe alloy, which facilitated the lithiation/
delithiation processes. However, its capacity decreased significantly to
311 mAh g−1 over 200 cycles. The introduction of the hybrid buffering
matrix of TiO2 and C to the ZnTe composite resulted in considerable
enhancements in the specific capacity and cyclic stability. Specifically,
the ZnTe-TiO2-C electrode delivered a highly stable specific capacity of
5
Applied Surface Science 509 (2020) 144718
611 mAh g−1 over 300 cycles, corresponding to 95% capacity retention
(compared with its capacity at the second cycle). This was mainly due
to the homogeneous dispersion of nanocrystalline ZnTe in the efficient
buffering hybrid matrix of the TiO2 and the amorphous C matrix. A
slight increase in capacity was observed with the increasing cycle
number, which is ascribed to the late activation of embedded active
particles in the composites [31,32]. The TiO2 functioned not only as an
active phase but also as a supplementary buffering material [28]. As
shown in Fig. 6b, the long-term cyclic performance of these electrodes
measured at 0.5 A g−1 exhibited a similar trend to the cyclic perfor-
mance measured at 0.1 A g−1 although the capacities were generally
reduced. The ZnTe-TiO2-C electrode displayed the best performance; a
specific capacity of 492 mAh g−1 at 500 cycles, which was much higher
than those of the ZnTe-TiO2 and ZnTe-C electrodes (139 and
382 mAh g−1, respectively). The superior cyclic performance of ZnTe-
TiO2-C is ascribed to the exisitence of the TiO2-C hybrid matrix into the
ZnTe alloy, which reduced the stresses and strains of ZnTe particles and
prevented the aggregation of active ZnTe during continuous electro-
chemical reactions. Additionally, the excellent structural stability of
TiO2 with very small volume changes (~3%) during the lithiation/de-
lithiation processes contributed to the cyclic stability of the composite.
The rate capabilities at different current densities from 0.1 A g−1 to
10 A g−1 are shown for three electrodes, as presented in Fig. 6c. The
ZnTe-TiO2 and ZnTe-C electrodes exhibited relatively poor rate cap-
ability, delivering low capacities of 134 and 302 mAh g−1, respectively,
at 10 A g−1. By contrast, the ZnTe-TiO2-C electrode presented an ex-
cellent rate performance with the higher specific capacities at all cur-
rent densities, delivering specific charge capacities of ~539, ~501,
~487, ~455, and ~435 mAh g−1, respectively, at 0.1, 0.5, 1, 3, and
5 A g−1. In addition, ZnTe-TiO2-C retained a high specific capacity of
~406 mAh g−1 even at high current density of 10 A g−1, corresponding
Q.H. Nguyen, et al.
Fig. 6. (a) Cyclic performances at 0.1 A g−1; (b) long-term cyclic performance at 0.5 A g−1; (c) rate capability; (d) EIS spectra of the ZnTe-TiO2-C, ZnTe-TiO2, and
ZnTe-C electrodes after 50 cycles.
to ~76% of its initial capacity at the current density of 0.1 A g−1. This
good rate performance suggests the facile Li+ ion transport in the ZnTe-
TiO2-C electrode, which are associated with the homogeneous dis-
tribution of nanosized ZnTe in the conductive TiO2-C matrix preventing
the aggregation of ZnTe particles under fast charge/discharge cycling.
To evaluate the enhanced electrical conductivity of ZnTe-TiO2-C com-
pared with the ZnTe-TiO2 and ZnTe-C electrodes, EIS measurements
were conducted for these three samples after 50 cycles at 0.1 A g−1, as
shown in Fig. 6d. Among the three electrodes, ZnTe-TiO2-C exhibited
the smallest semicircles and the lowest charge transfer resistance (Rct)
after 50th cycle (detailed data are presented in Table S1). These results
suggest that the TiO2-C introduction as a hybrid buffering matrix pro-
vided efficient electron-transport pathways for the active particles and
stabilized the thin SEI layer, enhancing the electric conductivity of the
composite.
3.3. Electrochemical performance of ZnTe-TiO2-C//LiFePO4-G full cell
To investigate the practical application of the ZnTe-TiO2-C nano-
composites in a LIB system, we constructed a coin-type full-cell LIB
using LFP@G and ZnTe-TiO2-C as the cathode and anode, respectively,
as shown in Fig. 7. The electrochemical performance of the full cell was
measured in the potential range of 1.0–3.8 V at 0.1 A g−1. The mass
ratio between the cathode and anode was controlled to be ~1:2, con-
sidering their capacity balance. Fig. S4 shows a schematic principle of
ZnTe-TiO2-C//LFP@G full-cell LIB operation. Briefly, Li+ ions transfer
from ZnTe-TiO2-C anode to LFP@G cathode during the discharge pro-
cess, while Li+ ions move back from LFP@G to ZnTe-TiO2-C upon
charge process. As shown in Fig. 7a, the charge/discharge potential
profile of the ZnTe-TiO2-C//LFP@G full cell displayed an apparent cell
potential at ~2.5 V, corresponding to the difference in the main
6
Applied Surface Science 509 (2020) 144718
reaction potential between cathode and anode. The specific capacity of
the ZnTe-TiO2-C//LFP@G full cell was evaluated based on the sum-
mation of cathode and anode mass. The specific capacity of the full cell
was measured to be as high as ~81 mAh g−1 even after 200 cycles
(Fig. 7b). Remarkably, after the first cycle, the CEs of the full cell were
~100%, without significant capacity fading until 200 cycles. The rate
performance measurement showed the specific capacities of the ZnTe-
TiO2-C//LFP@G full cell as ~97, 65, 53, and 38 mAh g−1 at 0.1, 0.5, 1,
and 3 A g−1, respectively (Fig. 7c). Upon a series of different current
density and resuming to the original current density of 0.1 A g−1, the
recovery of capacity retention was as high as ~84% (~81 mAh g−1),
representing the excellent reversibility and good rate performance of
the ZnTe-TiO2-C//LFP@G full cell. The energy densities of the full cell
for ZnTe-TiO2-C//LFP@G estimated using the operational voltage of
2.5 V at different current rates were ~242, 163, 132, and 95 Wh kg−1,
respectively, at various current densities of 0.1, 0.5, 1, and 3 A g−1
(Fig. 7d). Notably, the energy density of the full cell (ZnTe-TiO2-C//
LFP@G) measured at 0.1 A g−1 exceeded that of a previously reported
Li4Ti5O12//LiFePO4 full cell (energy density of ~140 Wh kg−1) [47].
4. Conclusion
We demonstrated a ZnTe-TiO2-C nanocomposite prepared via a
simple and low-cost HEMM as a high-performance anode for LIBs. The
ZnTe-TiO2-C nanocomposite comprising of intermetallic ZnTe uni-
formly distributed in a multifunctional hybrid matrix of rutile TiO2 and
C exhibited great electrochemical performance because of many bene-
ficial features including microstructure that is efficient to Li+ ion
transport, high electronic conductivity, and the hybrid buffering effect
of the rutile TiO2 and amorphous C matrix for active ZnTe during cy-
cling. Compared with ZnTe-TiO2 and ZnTe-C electrodes, the ZnTe-TiO2-
Q.H. Nguyen, et al.
Fig. 7. Full-cell performance obtained using ZnTe-TiO2-C as an anode and LFP@G as a cathode: (a) GCD profiles at 0.1 A g−1 over the voltage range of 1–3.8 V; (b)
cyclic performance at 0.1 A g−1; (c) rate capability; and (d) energy density of the ZnTe-TiO2-C//LFP@G full cell at different current rates.
C electrode showed a highly reversible capacity of 611 mAh g−1 until
300 cycles, with an excellent capacity retention of 95%, and an superior
rate performance at high current density of 10 A g−1 (76% capacity
retention of its capacity at 0.1 A g−1). Furthermore, the ZnTe-TiO2-C
electrode delivered a good specific capacity of ~492 mAh g−1 over 500
cycles even at 0.5 A g−1. Furthemore, the electrochemical reaction
mechanism revealed by ex situ XRD analysis ensured the progressive
lithiation/delithiation processes of the active ZnTe and TiO2 phase
during cycling. Overall, ZnTe-TiO2-C nanocomposite can be an alter-
native anode material for high-performance rechargeable LIBs.
CRediT authorship contribution statement
Quoc Hanh Nguyen: Methodology, Investigation, Data curation,
Writing - original draft. Quoc Hai Nguyen: Conceptualization,
Investigation, Visualization. Jaehyun Hur: Conceptualization, Writing
- review & editing, Supervision, Project administration, Funding ac-
quisition.
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). It was also supported by the Korea Electric Power
Corporation (grant number: R18XA02).
7
Applied Surface Science 509 (2020) 144718
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.144718.
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