Chemical Engineering Journal 399 (2020) 125826

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Chemical Engineering Journal

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Mechanochemical synthesis of InP nanoparticles embedded in hybrid T

conductive matrix for high-performance lithium-ion batteries
⁎ ⁎
Quoc Hai Nguyena,1, Seongjoon Sob,1, Quoc Hanh Nguyenb, Il Tae Kimb, , 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 13120, Republic of Korea

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• mechanochemical
InP@TiO -C was synthesized via a
2
process for the first
time.
• effective
A hybrid TiO -C matrix served as an
2
buffer layer for InP during
cycling.
• Detailed mechanism was thoroughly
investigated with ex situ XRD, TEM,
SEM, and XPS.
• mance
InP@TiO -C showed
2
(~750 mAh g −1
good perfor-
at 1 A g−1
after 800 cycles).

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

Keywords: InP nanoparticles distributed in a TiO2-C hybrid matrix (InP@TiO2-C) are proposed as a promising anode ma-
InP terial for Li-ion batteries. A primary mechanochemical process on the precursor materials (In2O3, Ti, and P) leads
TiO2 to the formation of InP and TiO2 nanocrystal particles. The introduction of carbon during secondary ball milling
Carbon results in the formation of InP nanoparticles that are embedded in the TiO2-C hybrid conductive matrix
Anode
(InP@TiO2-C); this is confirmed by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy
Lithium-ion storage
(SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive
X-ray characterizations. As an anode material, InP@TiO2-C exhibits impressive electrochemical performance in
both half- and full-cell batteries. Various ex situ analyses including XRD, high-resolution TEM (HRTEM), and XPS
were synergistically used to demonstrate the mechanism of lithium-ion storage for the InP@TiO2-C electrode
during the electrochemical reaction, and to elucidate the roles of active InP particles and the TiO2-C buffering
hybrid matrix. Consequently, as an anode for half-cell batteries, the InP@TiO2-C delivers a high reversible
capacity (~850 mAh g−1 after 120 cycles at 0.1 mA g−1), excellent life span at 0.5 A g−1 (~750 mAh g−1 after
800 cycles), and high rate capability (85% capacity retention at 10 A g−1 compared with that at 0.1 A g−1).
Moreover, as an anode for practical full-cell batteries with LiFePO4@graphite cathodes, it delivers a promising
initial energy density of 214 Wh kg−1 (based on the total mass of the anode and cathode) and a good stability
(retention of 61%) over 150 cycles.

⁎
Corresponding authors.
E-mail addresses: itkim@gachon.ac.kr (I.T. Kim), jhhur@gachon.ac.kr (J. Hur).
1
Q. H. Nguyen and S. J. So contributed equally to this study.

https://doi.org/10.1016/j.cej.2020.125826
Received 6 April 2020; Received in revised form 27 May 2020; Accepted 6 June 2020
Available online 11 June 2020
1385-8947/ © 2020 Published by Elsevier B.V.
Q. Hai Nguyen, et al.
1. Introduction
Although Li-ion batteries (LIBs) have been extensively researched
over the past two decades, researchers continue to pay more attention
to them owing to their high energy densities and output voltages
compared with other energy storage systems [1–3]. Recently, numerous
anode materials for Li-ion storage, such as carbon-based, silicon-based,
alloy-based, metal oxide-based, and layer material-based compounds
[4–23] have been explored, with the main focus being overcoming the
drawbacks of LIBs, including low capacity, cyclic instability, poor rate
capability, energy density limitation, and poor safety [24,25]. Although
previous studies have proposed several potential anode materials for
LIBs, these materials are still far from being satisfactory for next-gen-
eration energy storage systems. Therefore, discovering new anode
materials for Li-ion storage systems continues to be of importance for
researchers.
Owing to their unique physical and chemical properties, metal
phosphide (MP) compounds have potential applications in energy sto-
rage, electronics, optoelectronics, and as catalysts [26,27]. Several MP
compounds, such as CuP2, Cu3P, GeP, Sn4P3, Co2P, Ni2P, LaP, and InP,
have been studied for LIBs and sodium ion batteries (SIBs) [28-34].
These MP compounds have been demonstrated to exhibit higher spe-
cific capacities (440–1750 mAh g−1, Table S1) than the theoretical
capacity of the commercial graphite electrode (372 mAh g−1 [35]).
Furthermore, they have long life spans and small electrode polariza-
tions. Therefore, they are considered promising candidates for next-
generation electrodes in LIBs. However, they still have shortcomings,
such as particle pulverization and large volume expansion, which re-
main to be resolved.
Among the many different MP compounds, InP is a significant
candidate for high-performance Li-ion storage owing to the conversion
reaction of Li ions with both In and P components. Its theoretical spe-
cific capacity is estimated to be ~ 735 mAh g−1 based on the overall
electrochemical reaction of InP + 4Li+ + 4e− → LiIn + Li3P, with the
nF
formula CInP = M (where CInP, n, F, and M denote the theoretical spe-
cific capacity of InP, number of electrons involved in the reaction,
Faraday’s constant, and molecular weight of InP, respectively) [36-38].
Although InP has been widely studied in various optoelectronics de-
vices such as high-speed electronics, lasers, photovoltaics, photo-
detectors, and photo-electrochemical devices because of its exciting
electrical properties [39–48], there are only a few studies on its energy
storage applications. Cui et al. first demonstrated the feasibility of an
InP thin film fabricated by pulsed laser deposition as an anode material
for LIBs with a reversible discharge capacity of ~620 mAh g−1 [36].
Gerngross et al. fabricated a single-crystalline porous InP anode with a
maximum possible capacity of ~800 mAh g−1 [37]. However, the cycle
lives demonstrated in those studies were very short (~10 cycles). In
2018, Liu et al. improved the electrochemical performance of InP (a
specific capacity of ~690 mAh g−1 after 100 cycles) by introducing
reduced graphene oxide (rGO) to synthesize InP/rGO [38]. Never-
theless, InP/rGO showed continuous capacity fading from an initial
discharge capacity of 1872 mAh g−1, and no strategy was presented to
overcome this problem. Although all these InP-based composites have
consistently demonstrated the possibility of InP as a potential high-
performance anode, more in-depth studies are required to further im-
prove its electrochemical performance by the rational design of InP-
based materials.
Carbon is one of the most commonly used buffering materials owing
to its desirable characteristics such as low cost, easy processability,
chemical stability, and high conductivity, with reasonably low con-
tribution to the total capacity (theoretical capacity of 372 mAh g−1
based on the reaction with Li to form LiC6) [4,49–51]. Furthermore,
TiO2 as a crystalline buffering material has remarkable properties si-
milar to graphite, including low toxicity, low cost, and high safety. It
has been widely used as an inactive and active material in LIBs owing to
its excellent cyclic stability and small volume change (3–4%) with a
2
Chemical Engineering Journal 399 (2020) 125826
reasonable level of theoretical capacity (335 mAh g−1) that is close to
that of graphite [52-58]. Because of these attractive features, TiO2 has
been widely used in couple with various active materials such as Si,
SnO2, Fe2O3, and CoO [55,59–61].
In this study, we firstly propose the solid-state synthesis of InP via a
simple, fast, and scalable mechanochemical ball milling process for a
new anode material in lithium-ion batteries (LIBs). Various character-
izations (X-ray diffraction (XRD), Raman spectroscopy, X-ray photo-
electron spectroscopy (XPS), scanning electron microscopy (SEM),
high-resolution transmission electron microscopy (HRTEM), and en-
ergy-dispersive spectroscopy (EDS)) reveal that a ball milling of pow-
ders (In2O3, Ti, P, and C) produces well-defined binary crystals of InP
and TiO2 in amorphous C, which possesses an extremely favorable
structural feature for an anode in LIBs. This is because the hybrid TiO2-
C matrix not only synergistically buffers the volume change in InP, but
also allows enhanced mechanical properties and better electrical con-
ductivity. Electrochemical measurements show that InP@TiO2-C has
excellent performance in terms of the specific discharge capacity (~850
mAh g−1 after 120 cycles at 100 mA g−1), cycle life (~750 mAh g−1
after 800 cycles at 500 mA g−1), and rate capability (85% capacity
retention at 10 A g−1 compared with that at 0.1 A g−1) for the half-cell
battery test. Moreover, as an anode for practical full-cell batteries, it
delivers a promising initial energy density of 131 Wh kg−1 and cyclic
stability (capacity retention of 61%) over 150 cycles. Therefore, we
provide an in-depth understanding of the reaction principle of the
InP@TiO2-C electrode and elucidate the roles of the individual con-
stituents in the nanocomposite.
2. Experimental section
2.1. Material synthesis
InP@TiO2-C was synthesized via two-step mechanochemical ball
milling. In the first milling step, In2O3 (1.48 g, 99.9%, Alfa Aesar), Ti
(0.38 g, 99%, Alfa Aesar), and red P (0.33 g, 99.99%, 325 mesh, Alfa
Aesar) powders along with zirconium oxide balls (44 g, diameters 3/8
and 3/16 in.) were placed in a zirconium oxide vessel reactor (80 ml)
under an Ar atmosphere. The input amounts of each powder were based
on the stoichiometry of the following solid-phase reaction:
2In2 O3 + 3Ti + 4P → 4InP + 3TiO2 (ΔGo = −1196kJ/mol) (1)
The above solid-state reaction is supposed to occur spontaneously
based on the calculation of change in free energy of reaction (see the
detailed calculations in Fig. S1). Ball milling (Pulverisette 5, Fritch) was
performed at 300 rpm for 10 h. In the second step, C (0.22 g, 99.99%,
Alfa Aesar) was added to the reactor followed by milling for 10 h to
synthesize InP@TiO2-C. InP@TiO2 (a control sample) was synthesized
following the same procedure but with only the first milling step. For
comparison, InP@C was also synthesized as another control sample
using two-step ball milling in which InP was first synthesized using In
(1.58 g, 99.99%, Alfa Aesar) and P powders (0.42 g, 98.9%, Alfa Aesar),
followed by C addition (InP : C = 7 :3, w:w).
2.2. Material characterization
XRD (D/MAX-2200 Rigaku, Japan) was used to determine the
formed phases of the as-prepared powders. XPS (Kratos AXIS Nova) and
micro Raman spectroscopy (ANDOR Monora500i, 633 nm) were per-
formed to characterize the structural information of as-prepared pow-
ders. The microscopic morphologies of the powders were observed by
SEM (Hitachi S4700, Japan) and HRTEM (TECNAI G2F30) in con-
junction with EDS. To study the Li-storage mechanism in a more precise
manner, various ex situ analyses (ex situ XRD, XPS, HRTEM, and SEM)
were performed, in which the powders were collected from the elec-
trode after a certain number of cycles.
Q. Hai Nguyen, et al.
2.3. Electrochemical characterization
A coin-type electrochemical half-cell battery (CR2032) was as-
sembled in an Ar-filled glove box, which contained an as-prepared
electrode as a working electrode, a lithium foil as a counter electrode,
polyethylene (PE) as a separator, and an electrolyte solution consisting
of 1 M LiPF6 in ethylene carbonate (EC)/diethylene carbonate (DEC)
(1:1 by v:v). To prepare a working electrode, a slurry was prepared by
mixing as-prepared active powders (InP@TiO2-C, InP@TiO2, and
InP@C), acetylene black, and polyvinylidene fluoride (PVDF) at a
weight ratio of 70:15:15 in an N-methyl-pyrrolidone (NMP) solvent.
The as-obtained slurry was then casted onto a Cu foil using a doctor
blade method, followed by subsequent drying in a vacuum oven at
70 °C for 12 h, and then punched into disk-shaped (12 mm diameter). A
battery cycler (WBCS3000, WonAtech) was used to perform the cy-
clability test in the voltage range of 0.01–3.0 V (versus Li/Li+) and the
rate capability test at various current densities (0.1, 0.5, 1, 3, 5, and 10
A g−1). Cyclic voltammetry (CV) and electrochemical impedance
spectroscopy (EIS) measurements were performed using a multichannel
electrochemical workstation (ZIVE MP1, WonAtech). The loading mass
of the active material was ~1 mg cm−2, and all calculations were based
on the mass of the active material of the anode (the mass of total
composite) for half-cell testing. For full-cell testing, a composite of
LiFePO4-graphite (LFP@G) was prepared as a cathode. LFP@G was
prepared via ball milling, in which a mixture of lithium iron phosphate
(LFP) (1.4 g, 97%, Sigma-Aldrich)) and graphite (G) (0.6 g, 99.9995%,
Alfa Aesar)) was milled for 12 h. The mass ratios between the anode
(InP@TiO2-C) and cathode (LFP@G) were 1:1.4 and 1:2 to balance the
capacity contribution from each electrode in a full cell. For both full
cells, the anode and cathode films were electrochemically pre-dis-
charged and pre-charged to remove the effects of SEI layer formation
and allow the batteries to attain a stable condition. The voltage window
applied for the full cell was 0–3.8 V (versus Li/Li+).
3. Results and discussion
Fig. 1a illustrates the mechanochemical synthetic scheme of the
InP@TiO2-C composite using two-step ball-milling. The crystalline
structure of InP@TiO2-C synthesized is consistent with the theoretical
crystal structures of its crystalline constituents (InP and TiO2) from XRD
patterns (Fig. 1b and Fig. S2). The XRD patterns of the synthesized
InP@TiO2-C composite confirm the formation of the cubic phase
structure of InP (PDF#32-0452) and tetragonal rutile phase structure of
TiO2 (PDF#21-1276) without traces of precursors of In2O3 (PDF#06-
0416), Ti (PDF#44-1294), and P (PDF#44-0906) in the as-obtained
powder. The crystalline structure of InP@TiO2 without added C is al-
most identical to that of InP@TiO2-C because of the amorphous nature
of C (Fig. S3). For InP@C synthesized using two step ball milling of In,
P, and C, the diffraction peaks were all matched with the InP phase (Fig.
S3). All these results confirm the successful synthesis of a target com-
posite material. Raman spectroscopy of InP@TiO2-C in Fig. 1c further
confirms the structural information of the constituents: stretching peaks
at ~137, 238, 399, and 594 cm−1 of rutile TiO2 correspond to the
symmetries of B1g, multi-photon process, Eg, and A1g, respectively
[62,63] and two other characteristic peaks observed at ~1335 and
~1600 cm−1 indicate the presence of carbon. As for the cubic structure
InP, there is no detectable Raman signal in the InP@TiO2-C nano-
composites because of the stronger signal from TiO2. This can be at-
tributed to either i) different scattering sensitivities between InP and
TiO2 or ii) surface enhanced Raman scattering (SERS) between InP and
C. Xiaodan et al. reported the Raman quenching of semiconducting ZnS
in the presence of TiO2. They attributed this phenomenon to extremely
sensitive Raman scattering from TiO2, which effectively reduces the
Raman active modes from ZnS [47]. However, Pan et al. demonstrated
the Raman peak quenching of ZnS when mixed with graphene because
of the SERS effect [48]. They attributed this phenomenon to the charge
3
Chemical Engineering Journal 399 (2020) 125826
transfer mechanism; the incident photons can cause a resonant charge
transfer between the semiconductor (ZnS) and adsorbate (graphene),
forming specific adsorbate–semiconductor complexes, which intensifies
Raman scattering from graphene while relatively reducing scattering
from ZnS. Because the resonance charge transfer between the semi-
conductor and carbon as the absorbate can originate from the induced
proton, the peak indicating the InP semiconductor is not detected in the
InP@TiO2-C nanocomposites [64-66]. To further validate the successful
formation of InP and TiO2 during the mechanochemical process, XPS
analysis of InP@TiO2-C was performed (Fig. 1d and Fig. S4). Two peaks
from In (3d1/2 at 445 eV and 3d3/2 at 452 eV) (Fig. 2d) and one peak
from P (2p at 129 eV) (Fig. S4b) represent the presence of InP in the
InP@TiO2-C composite [67]. In addition, two peaks from Ti (2p1/2 at
459 eV and 2p3/2 at 464.8 eV) (Fig. 2d) and one peak from O (2p at
531.7 eV) (Fig. S4d) confirm the formation of TiO2 in the as-prepared
InP@TiO2-C powder [68].
The SEM image of the InP@TiO2-C composite (Fig. 1e) exhibits a
uniform particle size (~50 nm), whereas InP@TiO2 and InP@C exhibit
a high level of size distribution (probably because of many aggregated
particles, Fig. S5). While most of particles are in the range of less
than 50 nm for InP@TiO2-C, InP@TiO2 and InP@C show broader size
distribution (Fig. S5c). The EDS analysis of InP@TiO2-C shows a
homogeneous distribution of InP, TiO2, and C in the as-obtained In-
P@TiO2-C composite (Fig. S6). The HRTEM (Fig. 1f) and corresponding
FFT image (Fig. 1g) of InP@TiO2-C demonstrate the presence of InP and
TiO2 crystal phases, which is consistent with the XRD, Raman, and XPS
results. A more detailed microstructure confirmed by the TEM and EDS
mapping images of InP@TiO2-C indicates the uniformly distributed
nanoparticles of InP and TiO2 embedded in amorphous C of the as-
prepared InP@TiO2-C composite (Fig. S7).
The Li-storage behavior of the as-prepared InP@TiO2-C anode was
studied by its galvanostatic discharge/charge profile (Fig. 2a), curren-
t–potential curves (CVs) during the first three cycles (Fig. 2b), and
crystal structure of each lithiation/delithiation state (Fig. 2c). The
electrochemical reaction mechanism of Li ions with InP follows the
multistep process as shown in Fig. 2c [36,38]. In brief, the first dis-
charge process (stage I in Fig. 2a and the peak at ~0.61 V in Fig. 2b)
represents the reaction between InP and Li+ to form In and Li3P
(InP + 3Li+ +3e− → In + Li3P; Eq. (2) below), corresponding to the
increasing specific capacity from 0 to ~430 mAh g−1. In stage II (dis-
charge from 0.5 to 0.1 V), a strong reduction in the peak is observed at
~0.2 V, indicating the reaction between In and Li+ to form InLi
(In + Li+ +e− → InLi; Eq. (3) below) with a significant capacity
contribution up to ~800 mAh g−1. In stage III (discharge from 0.1 to
0.01 V), the specific capacity continuously increases to ~1067 mAh
g−1, which can be attributed to the formation of the solid electrolyte
interphase (SEI) [38]. Meanwhile, during the first charge process, two
major oxidation peaks observed at ~0.72 and ~1.15 V are attributed to
the two reversible reactions (InLi → In + Li+ + e− and In + Li3P →
InP + 3Li+ + 3e−) as shown in Eqs. (4) and (5). The small anodic
peaks observed at 0.5, 0.76, and 1.5 V are related to the multistep
process of partial delithiation from InP (LixInP → LiyInP + zLi+, x
= y + z, Fig. S8) where the XRD peak at ~26° is shifted to a higher
angle due to the Li+ extraction from InP. In the first charge stage (stage
IV, from 0.01 to 0.8 V), the specific capacity increases to ~370 mAh
g−1, whereas in the second stage of charging (stage V, from 0.8 to
3.0 V), the capacity continuously increases to ~800 mAh g−1, in-
dicating full reversion except for the SEI formation. The overall elec-
trochemical reaction during the first discharge/charge process can be
written as:
Discharge:
InP + 3Li+ + 3e− → In + Li3P (2)
−
In + Li +
+e → InLi (3)
Charge:
Q. Hai Nguyen, et al.
Fig. 1. (a) Schematic of the formation of InP@TiO2-C. (b–e) XRD pattern, Raman spectra, deconvoluted In3d XPS profiles, SEM image, high-resolution TEM image,
and FFT image of as-prepared InP@TiO2-C nanocomposite, respectively.
InLi → In + Li+ + e− (4)
In + Li3P → InP + 3Li+ + 3e− (5)
Notably, there are no significant reduction/oxidation peaks that
correspond to the intercalation/deintercalation between Li-ions and
TiO2 or carbon, indicating that TiO2 and C mainly play the roles of
buffering materials for active InP during cycling. Because TiO2 delivers
a significantly low specific capacity of ~70 mAh g−1 at a current
density of 200 mA g−1 (Fig. S9) and small amount of TiO2 (~20 wt%) is
embedded in the InP@TiO2-C nanocomposite, its contribution to the
total specific capacity of the as-prepared anode is very small
[55,57,69,70]. More quantitatively, we can estimate the actual capacity
contribution from TiO2 in InP@TiO2-C is as low as 3% using the mea-
sured content (EDX analysis, Table S1) with the theoretical (or mea-
sured) capacity of InP, TiO2, and C, respectively (see the calculation in
Table S2). A comparison of the CVs and voltage profiles of InP@TiO2-C
with those of other as-prepared composites (InP@TiO2 and InP@C)
indicates a similar behavior (Figs. 2 and S9), demonstrating the similar
characteristics of InP despite the different synthesis routes.
For further insightful understanding of the lithiation/delithiation
mechanism of the InP@TiO2-C electrode, various ex situ characteriza-
tions were performed, including XRD, HRTEM, and XPS. The ex situ
XRD patterns (Fig. 3a), HRTEM images (Fig. 3b), and XPS profiles
(Fig. 4) of the InP@TiO2-C electrode material were obtained at various
cutoff potentials (discharges at 0.5 V (D-0.5 V), discharge at 0.01 V (D-
0.01 V), charge at 0.75 V (C-0.75 V), and charge at 3.0 V (C-3.0 V))
based on the reduction/oxidation peaks as shown in the CV curve
(Fig. 2b). Owing to the Cu current collector beneath the electrode
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Chemical Engineering Journal 399 (2020) 125826
material, two main diffraction peaks of Cu were observed in all samples
in the ex situ XRD analysis. At the open circuit potential (Fig. 3a-i), the
three main peaks observed at ~26.3°, 30.43°, and 43.6° correspond to
the (1 1 1), (2 0 0), and (2 2 0) lattice planes of InP (PDF#32–0452),
which is consistent with the characterization of the as-prepared powder
(Fig. 1b). However, the other peaks reflecting the presence of TiO2
could not be observed, which could be attributed to the strong peaks
from Cu, a relatively small amount of TiO2 in InP@TiO2-C, and the
presence of the PVDF binder that screens the diffraction peaks from
TiO2 [71]. The ex situ XRD pattern acquired at 0.5 V of the initial
discharge process (stage I in Fig. 3a-ii) indicates the appearance of In
(PDF#05–0642) and Li3P (PDF#04-0525) phases as well as a reduction
in peak intensities from InP when compared with those of the pristine
stage (Fig. 3a-i), which indicates that the reaction occurred according to
Eq. (2). An ex situ HRTEM image for the InP@TiO2-C electrode after
initial discharge to 0.5 V consistently shows the presence of the In (d-
spacing of 0.27 nm), InP phases (d-spacing of 0.34 nm), and Li3P (d-
spacing of 0.209 nm) (Fig. 3b-i) corresponding to the crystal planes of
In (1 0 1), InP (1 1 1), and Li3P (1 0 3) which are consistent with the ex
situ XRD result shown in Fig. 3a-ii. After the discharge process at 0.01 V
(Fig. 3a-iii), the XRD peaks at ~22.6° ((1 1 1) plane) and ~37° ((2 2 0)
plane) confirm the InLi phase (PDF#09–0066), demonstrating that the
In formed in stage I reacted with Li-ions to form the InLi phase (Eq. (3)).
This reaction is further validated by an HRTEM image (Fig. 3b-ii), in
which the crystal plane of the InLi ((2 2 0) plane with a d-spacing of
0.24 nm) is observed. In addition, the peak intensity of In strongly re-
duced, which is consistent with the reaction in Eq. (3). The residual InP
phase in stage II is confirmed by both, the ex situ XRD pattern (Fig. 3a-
iii) and HRTEM image (Fig. 3b-ii), which could be attributed to the
Q. Hai Nguyen, et al. Chemical Engineering Journal 399 (2020) 125826

Fig. 2. (a) Initial galvanostatic discharge/charge profile at 100 mA g−1. (b) Initial three cycle current–potential curves at scan rate of 0.2 mV s−1. (c) Crystal
structures of the corresponding lithiation/delithiation stages.

incomplete activation of active InP. To further confirm the highly re-
versible conversion of the delithiation process, the ex situ XRD patterns
(Fig. 3a-(iv and v)) and HRTEM images (Fig. 3b (iii and iv)) of the
electrode at 0.75 and 3.0 V of the initial charging cutoff potential were
obtained. After charging to 0.75 V, the InLi phase disappeared in both
the XRD pattern and HRTEM image, and the In peak in XRD increased
in intensity, as shown in Fig. 3a-iv, indicating the reversible reaction as
in Eq. (3). At the full-charging stage at 3.0 V, the ex situ XRD pattern
(Fig. 3a-v) and HRTEM image (Fig. 3b-iv) indicate the reappearance of
the InP phase and reduction of the In phase, suggesting the reversible

Fig. 3. (a) Ex situ XRD patterns and (b) ex situ HRTEM of InP@TiO2-C electrode collected at various cutoff potentials.

5
Q. Hai Nguyen, et al.
Fig. 4. Ex situ XPS profiles of InP@TiO2-C electrode collected at various cutoff potentials.
conversion as in Eq. (4). However, the InP peaks in XRD could not fully
recover their intensities after the full-charging process when compared
with the pristine stage, which could be attributed to the presence of the
irreversible SEI layer after lithiation. The lithiation mechanism was
further examined using ex situ XPS (Fig. 4). The deconvoluted In 3d
(left panel), P 2p (central panel), and Li 1s (right panel) profiles of the
InP@TiO2-C electrode measured at various cutoff potentials clearly
confirm the lithiation/delithiation mechanism revealed by the CV, ex
situ XRD, and ex situ HRTEM analyses. In brief, in stage I of D-0.5 V
(Fig. 4b), the XPS signals detected at ~443.7 eV in the In 3d spectra
(blue color in the left panel of Fig. 4b) indicate the typical state of metal
In (In0) [72,73]. The peak detected at 131 eV corresponds to the Li3P
phase (purple color in the central panel of Fig. 4b) [74]. Although InP
peaks are still observed in the deconvoluted spectrum in P 2p
(~129 eV), their intensities significantly decrease at the D-0.5 V
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Chemical Engineering Journal 399 (2020) 125826
discharged state (pink color in the P 2p spectrum in the right panel of
Fig. 4b) when compared with its pristine stage (pink color in the P 2p
spectrum in the central panel of Fig. 4a). In addition, Li 1 s spectra
indicate the Li3P alloy (purple color at 57 eV in the right panel of
Fig. 4b), decomposition of the electrolyte (brown color at 55.5 eV in the
right panel of Fig. 4b–4e), and residues of lithium metal (yellow color at
54 eV in the right panel of Fig. 4b–4e) [74]. These results could be
attributed to the reaction between InP and Li ions to form In and Li3P
(as in Eq. (2)). Fig. 4c exhibits the deconvoluted XPS peaks for D-0.01 V
with an increase in the peak intensity of InLi and Li3P (binding energies
of InP and InLi are the same [75]) as the D-0.5 V case), indicating the
continuous reduction of InP to In and Li3P and the reaction of In with Li
ions to form InLi (as in Eq. (3). Furthermore, the deconvoluted peak of
InP (pink color) at ~129 eV (Fig. 4c) is the residue, implying the in-
complete reaction of active InP, as discussed earlier. For C-0.75 V
Q. Hai Nguyen, et al.
Fig. 5. (a) Cyclic performances of InP@TiO2-C, InP@TiO2, and InP@C at current density of 100 mA g−1. (b) Long-term cyclic performance of InP@TiO2-C at high
current density of 500 mA g−1.
(Fig. 4d), although the deconvoluted XPS peaks corresponding to In and
Li3P phases persist, their intensities decrease, which is consistent with
the reaction in Eq. (4). Meanwhile, when charging to 3.0 V (Fig. 4e), the
peak of InP reappears with the disappearance of peaks from InLi and
Li3P, which indicates the highly reversible conversion process.
The cyclic performance was measured for three different synthe-
sized electrodes (InP@TiO2-C, InP@TiO2, and InP@C) at 100 mA g−1
in the potential range of 0.01–3.0 V (Fig. 5a). The initial coulombic
efficiencies (ICEs) of the InP@TiO2-C, InP@TiO2, and InP@C electrodes
were 75%, 84%, and 82% from the initial charge/discharge capacities
of 805/1067, 691/821, and 832/942 mAh g−1/mAh g−1, respectively.
The capacity decrease of initial three cycles for the InP@TiO2-C is
pronounced which may be associated with the gradual SEI layer for-
mation for hybrid TiO2-C buffering matrix; the coulombic efficiencies of
InP@TiO2-C were 90 and 93% for 2nd and 3rd cycle, respectively,
which were lower than those of InP@TiO2 (96% and 97%) and InP@C
(96 and 97%) as shown in Fig. S10. However, despite higher capacities
of InP@TiO2 and InP@C than that of InP@TiO2-C in initial several
cycles, their capacities gradually decreased and became less than 400
mAh g−1 after 120 cycles. Meanwhile, the InP@TiO2-C electrode
showed very stable and even slightly increasing capacity until the 250th
cycle (807 mAh g−1 with CE of 100% at the 250th cycle). This cyclic
stability could be attributed to the presence of the TiO2-C hybrid ma-
trix, which prevents the aggregation of InP particles and reduces the
stresses/strains of active InP particles, thereby avoiding the particle
pulverization caused by volume expansion during repeated lithiation/
delithiation processes [76]. The increasing capacity with the increase in
the number of cycles is associated with the gradual activation of the
active material and polymer/gel-like film formation during repeated
cycles [77–79]. This might be also associated with the reduced
7
Chemical Engineering Journal 399 (2020) 125826
polarization between two main cathodic and anodic peaks (from 1st to
200th cycle) which enhances the efficiency of charge transfer during
the discharge/charge process (Fig. S11) [80,81]. The long-term cyclic
performance of InP@TiO2-C measured at a high current density of
500 mA g−1 for 800 cycles (Fig. 5b) showed a behavior similar to the
case of low current density (0.1 A g−1); the specific capacity gradually
increased during initial 120 cycles and then remained steady until 800
cycles with a capacity of ~750 mAh g−1. We note that the similar
polarization reduction was observed for the capacity increasing region
(470–570 cycle, Fig. S12).[80,81] This result is superior to those for
most other metal phosphide-based anodes in previous works, as sum-
marized in Table S3.
The rate capabilities of three electrodes (InP@TiO2-C, InP@TiO2,
and InP@C) were measured at current densities of 0.1, 0.5, 1, 3, 5, and
10 A g−1 in the voltage range of 0.01–3.0 V as another important cri-
terion (Fig. 6a). For InP@TiO2, the specific capacities significantly de-
creased with an increase in current density (from ~600 mAh g−1 at
initial 0.1 A g−1 to ~200 mAh g−1 at 10 mA g−1) and did not fully
reverse after the current density returned to 0.1 A g−1 (~400 mAh
g−1). When compared with InP@TiO2, although InP@C showed higher
specific capacities at all current densities (~750, 700, 650, 600, 550,
and 500 mAh g−1 at 0.1, 0.5, 1, 3, 5, and 10 A g−1, respectively),
irreversible capacity recovery was still observed after returning to the
original current density. For InP@TiO2-C, the rate performance was
superior to that of other electrodes at all current densities; capacity
retentions were 97% (0.5 A g−1), 95% (1.0 A g−1), 88% (3.0 A g−1),
87% (5.0 A g−1), and 85% (10.0 A g−1) compared with the capacity at
0.1 A g−1. Particularly, when the current density was returned to 0.1 A
g−1 from 10 A g−1, the specific capacity rather slightly increased to
720 mA g−1 (120% when compared with the capacity at the initial
Q. Hai Nguyen, et al.
Fig. 6. (a) Rate capability and (b) EIS profiles of InP@TiO2-C, InP@TiO2, and InP@C after 35 cycles of rate capability testing. (c) Ex situ SEM images of InP@TiO2-C,
InP@TiO2, and InP@C after rate capability and EIS testing.
current density). This behavior is similar to the cyclic performance
(increasing capacity during 100 cycles in the cyclic performance in
Fig. 5 resulting from the continuous activation of the InP active mate-
rial and more polymer/gel-like film formation during the repeated cy-
cles). These results could be further understood by comparing Nyquist
plots and ex situ SEM measurements for the three electrodes after rate
capability measurements (Fig. 6b and c). The smallest semicircle radius
of InP@TiO2-C when compared with those of InP@TiO2 and InP@C
after rate capability measurement indicates the lowest charge transfer
resistance, which promotes electron and Li-ion transport in the elec-
trode [82,83]. Clearly, the combination of TiO2 and carbon as a buf-
fering hybrid matrix allows alleviated volume change and maintenance
of high conductivity, resulting in the prevention of InP particle pul-
verization from the large volume expansion during cycling. In line with
this, the low charge transfer resistance and high rate capability of In-
P@TiO2-C explain the observation in long-term cyclic performance at a
high capacity (Fig. 6b) where the capacity has been well-maintained at
0.5 A g−1 relative to the capacity at 0.1 A g−1. Ex situ SEM images of
the electrodes after rate capability testing further demonstrate the su-
periority of InP@TiO2-C, in that while many cracks and delaminated
parts were observed in InP@TiO2 and InP@C, the original morphology
was retained for InP@TiO2-C when comparing the images of all samples
before/after cycling (Fig. 6c and Fig. S13). Additionally, elemental
mapped images (Fig. S14) and EDS analysis (Table S4) reveal the uni-
form distribution of all the components without much change in the
ratio of all the constituent atoms; indicating the InP@TiO2-C maintain
8
Chemical Engineering Journal 399 (2020) 125826
its structure without much aggregations during the cycling.
Finally, the electrochemical performance of practical full-cell bat-
teries was measured with LFP@G as a cathode and synthesized
InP@TiO2-C as an anode at the current density of 100 mA g−1 (mass
ratio of 2:1 (cathode:anode)) in the potential range of 1.0–3.8 V
(Fig. 7a). The initial three voltage profiles of the full cell indicate a
nominal working voltage of ~1.7 V and ICEs of 95%, 97%, and 97%
from the charge/discharge capacities of 95/101, 94/97, and 92/95
mAh g−1/mAhg−1 for the 1st, 2nd, and 3rd cycles, respectively
(Fig. 7b). Fig. 7c shows the cyclic performance of the full cell with mass
ratios of 1.4:1 and 2:1 between the cathode and anode. The capacity of
the full cell was calculated based on the total mass of the anode and
cathode. It was found that the full cell with a mass ratio of 2:1 (cath-
ode:anode) showed superior cyclic behavior because of the increased
mass ratio of the cathode, which enabled more efficient contribution to
the capacity of full cells. In general, the specific capacity balance be-
tween cathode and anode (i.e., N/P ratio) is very important for the
efficient and balanced ion movement in the full cell. In most cases, since
the specific capacity of cathode is less than that of anode, the loading
amount of cathode should be higher than that of anode to optimize N/P
ratio. In our particular case, the specific capacity of cathode
(LiFePO4@G) was separately measured as ~130 mAh g-1 (Fig. S15),
which is much lower than that of anode (InP@TiO2-C, ~823 mAh g−1
in Fig. 5a). Because of this large specific capacity difference between
cathode and anode, when we applied higher mass ratio of cath-
ode:anode (2:1), the full cell showed higher capacities than the case of
Q. Hai Nguyen, et al.
Fig. 7. (a) Schematic of full-cell battery. (b) Voltage profile during three cycles. (c) Cyclic performance of InP@TiO2-C/LFP@G full cell at current density of
100 mA g−1.
lower mass ratio of cathode:anode (1.4:1) during the capacity entire
capacity range measured (150 cycles). Specifically, the full cell with a
2:1 mass ratio exhibited a capacity of 126 mAh g−1 at the first cycle
(corresponding energy density of 214 Wh kg−1) and 77 mAh g−1 at the
150th cycle (corresponding energy density of 131 Wh kg−1). This result
suggests that the InP@TiO2-C composite synthesized by the facile and
scalable mechanical-milling process can be a promising anode material
for the next generation of practical energy storage devices.
4. Conclusions
We demonstrated a novel InP@TiO2-C nanocomposite synthesized
using a facile two-step mechanochemical milling process. Various
characterizations (XRD, Raman, SEM, TEM, XPS, and EDX) confirmed
that InP@TiO2-C displayed a beneficial morphology as an anode for
LIBs; this is due to the fact that active InP nanoparticles were effectively
surrounded by the hybrid crystalline TiO2 and amorphous conductive
C. This hybrid conductive matrix of TiO2-C functioned as an efficient
buffering matrix for active InP when InP@TiO2-C was used as an anode
in LIBs. InP@TiO2-C exhibited excellent electrochemical performance
for both half- and full-cell batteries. When compared with InP@TiO2
(without adding C) and InP@C (ball milling of commercial InP and C),
the InP@TiO2-C nanocomposite showed superior performance in terms
of the specific capacity (~850 mAh g−1 after 120 cycles at
100 mA g−1), long life span (750 mAh g−1 after 800 cycles at
500 mA g−1), and rate performance (~97%, 95%, 88%, 87%, 85%, and
120% at 0.5, 1, 3, 5, and 10 A g−1, and returned 0.1 A g−1 of current
density, respectively, as compared with the capacity at an initial current
density of 0.1 A g−1). With regard to the practicality of the full cell, the
InP@TiO2-C anode delivered a promising initial energy density of 214
Wh kg−1 and a stability of as high as 150 cycles during cyclic perfor-
mance.
Declaration of Competing Interest
The authors declare that they have no known competing financial
9
Chemical Engineering Journal 399 (2020) 125826
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This research was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education (NRF-2019R1F1A1057709). This research
was also supported by Basic Science Research Capacity Enhancement
Project through Korea Basic Science Institute (National Research
Facilities and Equipment Center) grant funded by the Ministry of
Education (2019R1A6C1010016).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.125826.
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