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Arsenic for high-capacity lithium- and sodium-ion

Cite this: Nanoscale, 2018, 10, 7047
batteries†
Young Rok Lim,a Fazel Shojaei,b Kidong Park,a Chan Su Jung,a Jeunghee Park, *a
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Won Il Cho*c and Hong Seok Kang *d

Received 11th January 2018,
Accepted 10th March 2018
DOI: 10.1039/c8nr00276b
rsc.li/nanoscale
We report arsenic (As) as a promising alternative to graphite anode materials in lithium- and sodium-ion
batteries (LIBs and SIBs). The electrochemical properties of the As/carbon nanocomposite for both LIBs
and SIBs were investigated using experimental and theoretical approaches. The LIBs showed excellent
cycling performance, with a reversible capacity of 1306 mA h g−1 (after 100 cycles), which is much higher
than that of Li3As (1072 mA h g−1). In the corresponding SIBs, the measured reversible capacity was
750 mA h g−1 (after 200 cycles), which is lower than that of Na3As. Extensive first-principles calculations
were performed employing a structure prediction method for crystalline LixAs and NaxAs (x = 1–6) phases,
as well as ab initio molecular dynamics simulations for their amorphous phases. In good agreement with
the experimental LIB data, our calculations successfully predict the discharge capacity versus voltage
curves, showing that the capacity of the amorphous phase reaches up to that of Li4As. In contrast, the SIB
exhibited difficulty in reaching the predicted capacity (x = 3.5), probably due to significant volume expan-
sion. Comparison of the theoretical discharge curves with the experimental data provides valuable infor-
mation for the development of high-performance LIBs and SIBs.

1. Introduction As an attractive alternative to LIBs, sodium ion batteries

With the growing concern about global warming and the rapid
depletion of fossil fuels, the development of clean, sustain-
able, and renewable energy resources is a necessity. Therefore,
tremendous effort has been devoted to improving the energy
and power densities of electric energy storage devices such as
rechargeable batteries, fuel cells, and supercapacitors. Among
them, rechargeable lithium ion batteries (LIBs) have become
the dominant power sources for portable electronic devices,
and their usage has now been expanded to larger units such as
electric vehicles and robots, due to their high energy and
power densities.1,2 At the same time, there is serious concern
about the Earth’s limited lithium reserves, and the rapid devel-
opment and widespread use of lithium ion batteries may lead
to dramatic cost increases in the near future.
a
Department of Chemistry, Korea University, Jochiwon 339-700, Korea.
E-mail: parkjh@korea.ac.kr
b
Department of Bioactive Material Science, Jeonbuk National University, Chonju,
Chonbuk 560-756, Korea
c
Center for Energy Convergence, Korea Institute of Science and Technology,
Seoul 136-791, Korea. E-mail: wonic@kist.re.kr
d
Department of Nano and Advanced Materials, College of Engineering,
Jeonju University, Chonju, Chonbuk 560-759, Korea. E-mail: hsk@jj.ac.kr
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8nr00276b
(SIBs) have gained much attention because of the natural
abundance and low cost of sodium (Na).3–5 The similarities
between Li and Na intercalation chemistry allow for their use
in analogous materials; instead of using Li ions, Na ions can
transfer charge between anodes and cathodes, and the com-
ponents of LIBs can be reconfigured to be replaced by the SIB
components. However, the larger size of a Na ion (radius =
1.02 Å) as compared to a Li ion (radius = 0.76 Å) induces a
more significant volume expansion, which makes it difficult to
simply adopt recent strategies proposed for high-performance
LIBs, and consequently strongly limits their practical appli-
cations. Interest in exploring new electrode materials has dra-
matically increased in order to improve the low capacities,
poor rate capabilities, and low cycling stabilities of SIBs.
In recent years, phosphorus (P) has been found to be a very
promising anode material for both LIBs and SIBs.6–20 P is
known to have a higher theoretical capacity (2596 mA h g−1)
than graphite (370 mA h g−1) owing to the formation of Li3P
phase. In particular, orthorhombic phase (black) P showed
excellent battery performance because it has a unique layered
structure with good electrical conductivity. Arsenic (As), anti-
mony (Sb), and bismuth (Bi), which belong to the same group
as that of P (group V), consist of rhombohedral layered struc-
tures; these materials are usually referred to as “gray”. These
elements have been considered to be possible anode-material
candidates because they possess the same stoichiometric inter-

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calation as that of P.21–33 Although As is well known to be a
toxic and rare element, the theoretical capacity of As has been
predicted to be 1072 mA h g−1 (Li3As and Na3As), which is
higher than that of Sb (660 mA h g−1) and Bi (386 mA h g−1).
However, among the group V elements, As has been rarely
investigated. C. M. Park reported the electrochemical testing of
a LIB containing an As-carbon composite that demonstrated a
drastic decrease of capacity upon cycling despite a good rever-
sibility between the LiAs and As.21 Chen et al. reported that
FeAs exhibits a lithium storage capability through a conversion
reaction (FeAs + 3Li+ + 3e− → Li3As + Fe).34 However, these As
materials show poor electrochemical performance, and no
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definitive mechanism for the reaction of As with Li has been
established. Furthermore, to the best of our knowledge, the
cycling performance of SIBs containing As has not been
reported. Recently, the structure of an As monolayer (arsenene)
allotrope was predicted by Zeng’s group.35,36 Free-standing
rhombohedral phase arsenene was shown to be an indirect
bandgap semiconductor with a bandgap of 2.49 eV, while the
orthorhombic phase arsenene has a bandgap of 1.66 eV and
possesses a higher mobility up to 104 cm2 V−1 s−1.
Consequently, the layered structures of As have recently
attracted much attention because of their promising appli-
cation in electronic and optoelectronic devices.
Herein, we investigate the cycling performance of As in
both LIBs and SIBs, since these comparative studies will
improve our understanding of the electrochemical reactions
that occur at these As-containing electrodes. The As and
carbon (C) nanocomposites were synthesized using a ball-
milling method. The use of nanostructures can increase the
surface area and reduce the diffusion path length for Li or Na
ions, leading to a more efficient electrochemical reaction.
Furthermore, the C support forms a network that not only
ensures excellent electrical conductivity but also releases
volume-change stresses. Consequently, this material is
expected to reduce cycling performance degradation and
extend the battery life. Our LIBs and SIBs exhibit discharge
capacities of 1306 mA h g−1 (after 100 cycles) and 750 mA h
g−1 (after 200 cycles), which are higher and lower than
expected (1072 mA h g−1), respectively.
In order to explain the experimental results, we performed
extensive first-principles calculations employing a sophisti-
cated structure prediction method for crystalline lithiated/
sodiated As phases (LixAs and NaxAs with x = 1–6). Ab initio
molecular dynamics (MD) simulations were also carried out
for the amorphous phases. Various quantities were extracted
from these calculations, such as the formation energies, dis-
charge voltages, and volume changes accompanying the lithia-
tion and sodiation processes. Based on the detailed analyses
of these quantities, we demonstrate a good correlation
between the experimental and theoretical capacities of the LIB.
For the SIB, a higher capacity was determined theoretically
than was measured experimentally, for which a possible justifi-
cation is suggested. To the best of our knowledge, this work is
the first theoretical study on the LIB and SIB capacities of As
and helps to rationalize the experimental results.
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2. Experimental section
The As/C nanocomposite was prepared via a high-energy
mechanical milling (HEMM) of As (99%, Sigma Aldrich) and
graphite (90%) powders using a stainless steel jar for 24 h. As
powder (High Purity Chemicals, >99%, average size: 15 μm)
and stainless steel balls (diameter: 3/8 and 3/16 in.) were put
into a hardened steel vial having a capacity of 80 cm3 with a
ball to powder ratio of 20 : 1, and the HEMM process was con-
ducted at ambient temperature and pressure. The weight ratio
of As : graphite was 7 : 3. We also prepared separately the ball-
milled As and graphite powders.
The materials were characterized by scanning electron
microscopy (SEM, Hitachi S-4700), field-emission transmission
electron microscopy (FE TEM, FEI TECNAI G2 200 kV and Jeol
JEM 2100F), and energy-dispersive X-ray fluorescence spec-
troscopy (EDX). Fast Fourier-transform (FFT) images were gen-
erated by the inversion of the TEM images using Digital
Micrograph GMS1.4 software (Gatan Inc.). X-Ray diffraction
(XRD) pattern measurements were also carried out on a
Rigaku D/MAX-2500 V/PC X-ray diffractometer using Cu Kα
radiation (λ = 1.54056 Å). High-resolution XRD patterns were
obtained using the 9B and 3D beamlines of the Pohang Light
Source (PLS) with monochromatic radiation (λ = 1.54595 Å).
X-Ray photoelectron spectroscopy (XPS) measurements were
performed using the 8A1 beam line of the PLS with a photon
energy of 630 eV, as well as a laboratory-based spectrometer
(Thermo Scientific Theta Probe) using a photon energy of
1486.6 eV (Al Kα). Thermogravimetric analysis (TGA) was per-
formed using a TA Instruments Ltd SDT Q600 System. Samples
were heated in a flow of a N2/air mixture (100 sccm) at 10 °C
min−1 from room temperature to 900 °C.
For electrochemical tests, the electrodes of the battery test
cells were made of the active material, carbon black (Super P)
and polyacrylic acid (PAA, 35 wt% dissolved in water; Aldrich)
binder at a weight ratio of 6 : 2 : 2. The distilled water-mixed
slurry was coated onto the 10 mm-thick Cu foil. The coated
electrode was dried at 80 °C for 12 h and then roll-pressed.
The thickness of the film was 150 μm. The mass loading of
active materials on the electrode was 2 mg cm−2. The coin-type
half-cells (CR2032) were prepared in an argon-filled glove box.
The LIB cell consisted of an electrode (containing the active
material), the Li metal, a 25 μm microporous polyethylene
separator (Selgard 2400), and an electrolyte solution of 1 M
LiPF6 in 1 : 1 : 1 volume ratio of ethylene carbonate (EC), ethyl
methyl carbonate, and dimethyl carbonate (DMC).
Fluoroethylene carbonate (FEC) was used at 5 wt% as an elec-
trolyte additive. The SIB cells consisted of a sample electrode,
Na metal, glass fiber separator (Whatman grade GF/F binder
free glass microfiber, circle, 47 mm), and an electrolyte solu-
tion of 1 M NaPF6 in a 1 : 1 volume ratio of EC and diethyl car-
bonate and containing 5 wt% FEC additives.
Cyclic voltammetry (CV) measurements were conducted
(Biology SAS) in a voltage range of 0.01–3 V at a rate of 0.1
mV s−1. The performance of the cells was examined using a
battery testing system (Maccor 4000) at a current density of
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0.1–5 C between 0.01 and 3 V. We usually fabricated 3–5 LIB
(and SIB) cells for each composition, and took the data that
represent the average value. Electrochemical impedance spec-
troscopy (EIS, Solartron Multistat) measurements were carried
out by applying an AC voltage of 5 mV in the frequency range
of 100 kHz to 0.01 Hz. For the ex situ XRD measurements, the
cells charged or discharged to certain voltages were dis-
assembled in a glove box and the electrodes were rinsed
thoroughly in a DMC solution to remove LiPF6 (or NaPF6).
Structure-prediction calculations for crystalline LixAs and
NaxAs systems (x = 1–6) were performed using the CALYPSO
(Crystal structure AnaLYsis by Particle Swarm Optimization)
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program.37,38 At each stoichiometry, we employed CALYPSO to
generate ∼900 initial structures that included 1–6 formula
units (NU). Each of these structures was relaxed to a local
minimum on the potential energy surface (PES) using density
functional theory (DFT) implemented in the Vienna Ab initio
Simulation Package (VASP), as described below.39,40 By generat-
ing a large number of initial structures with distinct mor-
phologies, it is possible to widely cover the PES of the system.
As an example, we adopted supercells containing Li4As, Li8As2,
Li12As3, Li16As4, Li20As5, and Li24As6 formulas in order to gene-
rate initial structures for the Li4As stoichiometry. About 15
low-energy structures among the ∼900 initial structures were
then refined, during which the lattice parameters were also
optimized.
We next modeled amorphous LixAs and NaxAs according to
the melting–quench protocol using ab initio MD simulations.
First, we built an initial structure in a rectangular supercell
from which a large supercell was constructed using an appro-
priate repetition of the supercell of the most stable rectangular
crystalline phase in such a way that the three lattice para-
meters (a, b, c) were close to each other. A Nose–Hoover NVT
ensemble was simulated using MD runs with time steps of
1 fs.41–43 An energy cut-off of 350 eV was adopted, and the
k-point sampling was performed with the Γ point. At the first
stage of the MD simulation, the system was heated from 0 K to
2000 K at a rate of 1 K fs−1, followed by equilibration for 2 ps
at 2000 K. Following this, the system was cooled to 300 K at
1 K fs−1. Finally, it was equilibrated for 4 ps at 300 K. Three
structures were randomly chosen from the last 2 ps run, each
of which was fully optimized by also varying the lattice para-
meters following a standard procedure described in the next
paragraph. For further analysis at a specific stoichiometry, we
adopted the average of appropriate parameters of the three
optimized structures.
Standard geometry relaxations were performed using DFT
with the Perdew–Burke–Ernzerhof (PBE) exchange–correlation
functional, implemented in VASP.40 The electron–ion inter-
actions were described using the projector-augmented wave
(PAW) method, which is primarily a frozen-core all-electron
calculation.44 For structure optimization, atoms were relaxed
in the direction of the Hellmann–Feynman force using the
conjugate-gradient method with an energy cut-off of 400 eV
until a stringent convergence criterion (of 0.03 eV Å−1) is
satisfied.
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3. Results and discussion
The bulk As and graphite were ball milled for 24 h in an
As : graphite weight ratio of 7 : 3 using high-energy mechanical
ball milling. Thermogravimetric analysis (TGA) data confirmed
the ratio of As and C, as shown in Fig. S1.† The X-ray diffrac-
tion pattern of the material produced in this manner exhibited
peaks corresponding to the rhombohedral phase (R3 ˉm) of As
(JCPDS No. 72-1048, a = 3.759 Å and c = 10.547 Å) (Fig. S2†);
this ball-milled As and C composite nanomaterial is simply
referred to as “As/C”. X-Ray photoelectron spectroscopy was
employed to identify the composition and the electronic struc-
tures of As and C using fine-scanned peak analysis (Fig. S3†).
The results provide evidence that As–C bonded structures were
formed by the ball-milling process.
Fig. 1a displays the high-resolution electron transmission
microscopy (HRTEM) image of As/C, in which its general mor-
phology can be observed. The As nanoparticles, with an
average size of 20 nm, are homogeneously distributed through-
out the C matrix. Fig. 1b and the inset show the lattice-resolved
image and the corresponding fast Fourier transform (FFT)
image at the zone axis of the rhombohedral [0001], respect-
ively. The d-spacing between neighboring {110} planes (d110) is
1.9 Å and corresponds to that of As. The high-angle annular
dark-field (HAADF) image, scanning TEM (STEM) image, and
energy-dispersive X-ray fluorescence spectroscopy (EDX) maps
of the As L shell and the C K shell reveal that the nanoparticles
(NPs) are composed of elemental As, and these NPs are sur-
rounded by the C matrix (Fig. 1c). The corresponding EDX
spectrum confirm this As and C composition (Fig. 1d).
The electrochemical properties of As/C acting as the anode
material in a LIB were examined using coin-type half-cells. The
specific capacity (A h g−1) was calculated on the basis of the
mass of As by subtracting the capacity contribution of ball-mill
graphite in LIB (317 mA h g−1, Fig. S4†). The 1C rate is defined
as 1072 mA g−1, using the theoretical capacity of As. The
results are summarized in Tables S1 and S2.† The cyclic vol-
tammetry (CV) curves for the first ten cycles were obtained by
voltage scanning over the 0.01–3 V range at a rate of 0.1 mV s−1
(Fig. 2a). The first cycle shows a broad cathodic peak in the
0.2–0.5 V region, which is due to lithiation and the irreversible
formation of solid electrolyte interphase (SEI) layers. After the
first cycle, the reversible lithiation/delithiation signature of As
(As + xLi+ + xe− ⇌ LixAs) appeared consistently as a pair of
cathodic and anodic peaks at potentials of around 0.7 and
1.1 V, respectively. An anodic shoulder peak appears at 1.5 V,
probably due to another conversion reaction.
Fig. 2b show the voltage profiles for 1, 5, 10, 50 and 100
cycles at a discharge–charge rate (or current rate, C rate) of
0.1C (= 107 mA g−1), measured over the 0.01 to 3.0 V range. On
the basis of the half-cell reaction in this study, the insertion of
Li ions into the As electrode represents discharging, and the
extraction of Li ions from the electrode represents charging.
Fig. 2c shows the corresponding discharge–charge capacities
as a function of cycle number; the coulombic efficiency is also
plotted against the right axis.
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Fig. 1 (a) HRTEM image showing the general morphology of As/C. (b) Lattice-resolved TEM and FFT images (zone axis = [0001]) showing the rhom-
bohedral phase of As with d110 = 1.9 Å. (c) HAADF–STEM images and elemental maps of the As L shell and C K shell. (d) Corresponding EDX spectrum
showing that the samples are composed of As and C.
In the first discharge voltage profile, a plateau is observed
over a range of 0.2–0.5 V due to the lithiation and SEI layer for-
mation, which is consistent with the CV curve. After the first
cycle, the voltage profiles exhibit almost the same features for all
cycles. The discharge and charge curves show plateaus in the
0.7–0.9 and 1.0–1.2 V regions, respectively, consistent with the
CV curves. The discharge and charge capacities of the first cycle
are 1347 and 1087 mA h g−1, respectively, with an initial coulom-
bic efficiency of 82.0%. After the first cycle, the cell exhibits com-
plete capacity reversibility, with an average coulombic efficiency
of 98.3% for up to 100 cycles. Remarkably, the discharge capacity
of the 100th cycle is 1306 mA h g−1 (= Li3.7As). Furthermore,
there is about an 11% increase in the capacity from the fifth to
the 100th cycle. This rise in capacity has frequently been
observed in other anode materials and has been explained by
further activation of the active materials with cycling.45,46 This
result is explained by calculations, as discussed later.
The charge curves show a plateau region at 1.5 V, consistent
with the CV data. We measured the electrochemical perform-
ance in a narrower voltage range (0.01–1.5 V), as shown in
Fig. S5,† i.e., ∼1000 mA h g−1 after 50 cycles. The capacity
increases with increasing the voltage range, providing another
evidence for the conversion reaction at 1.5 V. All measure-
ments were carried out using 0.01–3 V.
Fig. 2d shows the discharge–charge capacities as a function
of cycle number (up to 200) at 1C and 2C rates. The initial cou-
lombic efficiencies are 73.4% (at 1C) and 71.8% (at 2C). After
the first cycle, the capacities are observed to be completely
reversible, with an average coulombic efficiency of 98.5 and
98.9% at 1C and 2C, respectively. The discharge capacity
gradually increases up to 120 and 160 cycles, respectively, after
which it decreases and reaches 770 and 786 mA h g−1 at the
200th cycle, respectively, corresponding to 58% and 60% of
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that at 0.1C rate (at the 100th cycle). Fig. 2e displays the dis-
charge–charge capacities as the C rate is changed in a stepwise
fashion, from 0.1C → 0.2C → 0.5C → 1C → 2C → 5C → 0.1C.
Ten discharge–charge cycles were performed at each C rate. As
the C rate reaches 5C, the capacity was observed to be 458
mA h g−1. It corresponds to nearly 40% of that at 0.1C rate
(at the 5th cycle). When the C rate returns back to 0.1C
(after the 60th cycle), the capacity returns to the slightly higher
value than that of the initial 0.1C rate step. Therefore, the As-
containing LIBs exhibit outstanding rate capabilities in
addition to the excellent reversibility of capacities.
Fig. 2f displays Nyquist plots resulting from electrochemical
impedance spectroscopy (EIS) measurements before the cycle
testing, and after the third and tenth cycles. The plots consist
of one semicircle in the high frequency region and a straight
line in the low frequency region. The equivalent-circuit (shown
in the inset) curve-fit analysis is detailed in Table S3;† Re is the
resistance of the electrolyte, Rct is the charge-transfer resis-
tance between the active materials and the electrolyte, RSEI is
the resistance of the SEI layers, ZW is the Warburg impedance
corresponding to the Li ion diffusion process, and CSEI and Cct
represent the constant-phase elements. Before cycle testing,
the diameter of the semicircle corresponds to Re = 2 Ω and
Rct = 400 Ω. After the first cycle, the size of the semicircle dra-
matically decreased, mainly due to a decrease in Rct: 43 and
37 Ω after the third and tenth cycles, respectively, and the
shape of the impedance spectrum changed due to the SEI for-
mation (RSEI). Data fitting provided Re = 3.0 Ω and RSEI = 14 Ω
for both impedance spectra. The electrical conductivity of the
activated As is expected to be much larger than that of the
initial As, which is associated with the decreasing Rct value.
These results suggest that the lower Rct of the activated As
material plays a major role in the large capacity of the LIB.
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Fig. 2 Cyclic voltammetry curves for the LIB over the first ten cycles. (b) Charge and discharge voltage profiles for 1, 5, 10, 50, and 100 cycles
determined between 0.01 and 3 V at a rate of 0.1C. Charge/discharge capacities (left axis) and coulomb efficiencies (right axis) vs. cycle number at
rates of (c) 0.1C, (d) 1C, and 2C. (e) Cycling performance with increasing rate (0.1C to 5C). (f ) Nyquist plots for the first ten cycles of the LIB. The
equivalent circuit diagram is shown in the inset.

In order to understand the role of graphite, we measured
the electrochemical properties of (1) ball-milled As, (2) ball-
milled graphite (C), and (3) a mixture of (1) and (2) with the
weight ratio of 7 : 3, as shown in Fig. S6, S4, and S7,† respect-
ively. The capacity of ball-milled As powders decreases dra-
matically upon cycling and the Rct values were much larger
than those of As/C. The LIB capacity of ball-milled graphite
was found to be 317 mA h g−1. The mixing of the ball-milled
As and C powders enhances significantly the capacity, which is
a similar value to that of As/C. The theoretical calculation pre-
dicts the same capacity as the experimental value, as will be
shown later. The C support could provide the network to facili-
tate the lithiation/delithiation, and increase the electrical con-
ductivity, reducing the charge transfer resistance. We expect
that the C support activates effectively the As nanoparticles,
which increases the capacity close to the calculated value.
Therefore, the active material was assumed to be As for the
As/C.
We next examined the electrochemical performance of As/C
as an anode material in a SIB, the results of which are sum-
marized in Tables S1 and S2.† The specific capacity was calcu-
lated using the mass of the As, since no capacity was observed
for only ball-mill graphite. The CV curves for this SIB exhibit a
broad cathodic peak in the 0–0.2 V region, and a sharp anodic

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peak at 0.7 V in the first potential sweep (Fig. 3a). The cathodic
peak is attributed to the activation of As and the formation of
SEI layers. After the first cycle, a pair of cathodic and anodic
peaks appear, consistent with the same current levels at poten-
tials of 0.2 and 0.7 V, respectively, which is a robust indication
of reversible sodiation/desodiation (As + xNa+ + xe− ⇌ NaxAs).
Fig. 3b shows the voltage profiles for 1, 5, 10, 50, and 100
cycles at 0.1C rate, determined between 0.01 and 3.0 V. The
first discharge and charge capacities are 990 and 716 mA h g−1,
respectively, with an initial coulombic efficiency of 72.3%. The
discharge and charge curves exhibit plateau regions at approxi-
mately 0.2 V and 0.7 V, respectively, in all cycles, due to the
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reversible sodiation/desodiation reaction of As. Fig. 3c shows
the corresponding discharge–charge capacities as a function
of cycle number (up to 200 cycles). After the first cycle, the cell
exhibits excellent reaction reversibility, with an average cou-
lombic efficiency of 99.3% up to 200 cycles. The discharge
capacity is 750 mA h g−1 after 200 cycles, and corresponds to
Na2.1As. The decrease in capacity after the first cycle is prob-
ably due to degradation of the electrode that originates from
significant volume expansion, as will be discussed later using
the computational results. The discharge capacity gradually
increases to 750 mA h g−1, increasing by 6% over 5–200 cycles,
but is negligible compared to that of the LIB.

Fig. 3 Cyclic voltammetry curve (scan rate = 0.1 mV s−1) for the SIB over the first ten cycles. (b) Charge and discharge voltage profiles for 1, 5, 10,
50, and 100 cycles determined between 0.01 and 3 V, at a rate of 0.1C, and (c) the corresponding capacities (left axis) and coulomb efficiencies
(right axis) vs. cycle number. (d) Cycling performance with increasing rate (0.1C to 5C). (e) Nyquist plots for the first ten cycles of the SIB. The equi-
valent circuit diagram is shown on the right.

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The rate capability and stability were tested by increasing
the C rate from 0.1C to 5C and then returning it back to 0.1C.
Fig. 3d displays the discharge–charge capacities as the C rate
changes by seven steps. As the C rate reaches 2C and 5C, the
discharge capacity was observed to decrease to 645 and
500 mA h g−1, respectively, corresponding to 91% and 70% of
0.1C (after the first cycle). After the 60th cycle, and the C rate
returns back to 0.1C, the capacity is fully restored to 740 mA h g−1.
Therefore the As-containing SIBs exhibit excellence per-
formance in the rate capability. Fig. 3e shows Nyquist plots
resulting from the EIS measurements before the cycle testing,
and after the third and tenth cycles. The equivalent-circuit
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need to find more definite evidence for this possibility, so we
leave this issue to a future work. Another possibility is that the
capacity of As is different from Li3As or Na3As, which have
been predicted until now. To shed light on this problem, we
performed theoretical-capacity calculations as detailed below.
First of all, we calculated the formation energy (Ef ) of the
lithiated/sodiated As phases (LixAs and NaxAs), according to
the equation: Ef (LixAs) = [Etot (LixAs) − x × (Li) − (As)], where
Etot (LixAs) is the total energy of the crystalline or amorphous
LixAs phase, (Li) is the chemical potential of a Li atom
obtained from its body-centered cubic (bcc) phase Li crystal,
and (As) is the chemical potential of an As atom obtained from

curve-fit analysis (shown in the inset) is provided in Table S3.† the rhombohedral phase As (gray) crystal. We assume that the
Before cycle testing, this fitting provided Re = 2.0 Ω and Rct = discharge voltage can be calculated using the centered-differ-
540 Ω. After the first cycle, the size of the semicircle decreased ence scheme: VE(LixAs) = (Li) − [Etot (Lix+1As) − (Lix−1As)]/2,
dramatically. The Rct value was reduced to 96 and 88 Ω after which adopts the average of the left and right slopes as the
the third and tenth cycles, respectively; Re = 4.4 Ω and RSEI = slope of energy with respect to x. Ef and VE are similarly
8.0 Ω were obtained for both impedance curves. For compari- defined for NaxAs.
son, we examined the electrochemical properties of the ball- Volume expansion accompanied by the lithiation is defined
milled As in the SIBs, the results of which are shown in by: ΔV/V = (V − V0)/V0, where V and V0 are the volumes of LixAs
Fig. S8.† The capacity decreased dramatically upon cycling and As, respectively. Another measure of the volume change is
(<100 mA h g−1 after 50 cycles at 0.1C), which is similar to that the stepwise volume contraction of LixAs given by: δV =
observed for the LIBs. The Rct values were larger than those of V(LixAs) − [V(Lix−1As) + V(Li)], where V(LixAs) and V(Lix−1As)
As/C. As the ball-milled As was mixed with the ball-milled are the volumes of LixAs and Lix−1As, respectively, while V(Li)
graphite, the capacity dramatically increases with excellent is that of a Li atom in a bcc Li crystal. An investigation into
cycling performance (Fig. S9†). Once again, the SIB perform- whether or not this parameter correlates with the ease of each
ance of As was greatly enhanced by the graphite support. lithiation step is a valuable exercise. It will be valuable to inves-
Ex situ XRD patterns were obtained for the As/C electrodes tigate if this parameter correlates with the ease of each lithia-
after applying various discharge/charge potentials, showing no tion step. A larger value of |δV| indicates a larger structural
crystalline phase after the first discharge step (Fig. S10†). The rearrangement during lithiation, which is more difficult to
HRTEM images revealed that the size of nanoparticles achieve at a higher C rate. The two quantities for NaxAs are
decreases significantly to 3–4 nm (LIB) and 1–2 nm (SIB) after defined in a similar way.
the first cycle (Fig. S11†). Based on the XRD and TEM images, The values of Ef, VE, ΔV/V, and δV for LixAs and NaxAs are
we suggest that the nanoparticles undergo a progressive amor- listed in Tables 1 and 2, respectively. Table S4† summarizes
phization upon cycling. the cell parameters of the most stable crystalline LixAs and
The experimental results are summarized as follows: (1) the NaxAs phases, where each crystal structure was obtained by a
LIB in this study exhibits a reversible capacity of 1306 mA h g−1 sequence of procedures for structure prediction and optimiz-
(= Li3.7As) at 0.1 C after 100 cycles; (2) the SIB exhibits a
reversible capacity of 750 mA h g−1 (= Na2.1As) at 0.1 C after
200 cycles; (3) the LIB exhibits a significant increase of Table 1 Various parameters for the crystalline (C) and amorphous (A)
capacity upon cycling, with a 15% increase over 5–100 cycles at phases of LixAs
0.1C. The anode potential of lithiation (sodiation) and
delithiation (desodiation), 0.7 and 1.1 V versus Li metal, 0.2 Phase x Efa (eV) VEb (V) ΔV/Vc (%) δVd (Å3)
and 0.7 V versus Na metal, respectively, is higher than that of C 1 −1.03 1.06 44.2 −9.56
graphite, but comparable to those of the other group V 2 −2.12 0.98 103.9 −6.22
3 −3.06 0.48 181.9 −2.30
elements.6–33 The high anodic potential could be a critical dis- 4 −2.92 −0.10 224.9 −9.89
advantage for fabricating high energy batteries.12 5 −2.85 −0.05 294.6 −3.94
To explain the higher capacity of the LIB, one possibility is 6 −2.82 −0.02 391.6 1.67
that electrochemical reactions of AsOx phases, namely (i) AsOx + A 1 −0.89 1.01 46.9 −7.87
2xLi+ + 2xe− ⇌ As + xLi2O and (ii) As + 3Li+ + 3e− ⇌ Li3As, 2 −1.86 0.88 98.8 −6.64
are involved that increase the capacity of the LIB. If we assume 3 −2.67 0.41 154.9 −5.71
4 −2.64 −0.01 226.8 −1.90
that x = 1 in process (i), then the theoretical capacity is 5 −2.65 −0.03 293.5 −3.17
1473 mA h g−1. The oxidation peak of the CV curve and the 6 −2.58 −0.03 377.9 1.11
plateau in the voltage profile at 1.5 V may correspond to a sig- a
Formation energy per Li atom. b Discharge voltage of the LIB.
nature of the reaction (i). On the other hand, the oxide form c
Volume expansion (%) accompanying lithiation with respect to As.
does not participate in sodiation/desodiation reactions. We d
Volume change in the stepwise Lix−1As + Li → LixAs process.

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 View Article Online

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Table 2 Various parameters for the crystalline (C) and amorphous (A) listed in Table S5.† The structures of crystalline and amor-
phases of NaxAs phous phases of LixAs and NaxAs (x = 0–6) are displayed in
Fig. S12.† Fig. 4 displays the plots of Ef, VE, ΔV/V, and δV
Phase x Efa (eV) VEb (V) ΔV/Vc (%) δVd (Å3)
against x for LixAs and NaxAs. Fig. 5 displays the structures of
C 1 −0.75 0.62 119.6 −8.97 Li4As and Na2As in their crystalline and amorphous phases,
2 −1.24 0.55 225.4 −14.21
3 −1.83 0.19 343.6 −10.43
4 −1.60 −0.21 505.7 −0.84
5 −1.40 −0.19 670.6 −0.28
6 −1.20 −0.20 936.5 21.59

A 1 −0.65 0.66 96.8 −12.73

2 −1.14 0.46 200.5 −11.05
3 −1.53 0.14 308.4 −10.07
4 −1.44 −0.11 454.5 −0.89
Published on 12 March 2018. Purchased by bizperu@gmail.com on 22 June 2022.

5 −1.35 −0.13 605.1 0.20

6 −1.20 −0.26 782.2 6.59
a
Formation energy per Na atom. b Discharge voltage of the SIB.
c
Volume expansion (%) accompanying sodiation with respect to As.
d
Volume change in the stepwise Nax−1As + Na → NaxAs process.

ation, as described in the Experimental section. The coordi-

nation number of As atoms within a radius of 3.0 Å increases
from 8 to 14 with increasing Li concentration, which is also
the same case for the amorphous phase. We next provide an
explanation for how an amorphous phase is generated using
the Li2As system as an example. A rectangular unit cell is first
built based on hexagonal crystals. Next, a larger supercell is
constructed that consists of (2 × 2 × 5) unit cells. A series of
Fig. 5 Structures of Li4As in (a) crystalline (top view) and (b) amorphous
MD simulations are then performed, followed by refining DFT phases, and those of Na2As in (c) crystalline (side view) and (d) amor-
calculations, as has been successfully applied to batteries.47–49 phous phases. Burgundy, light brown, and greenish yellow colors rep-
The optimized cell parameters of the amorphous phase are resent As, Li, and Na atoms, respectively.

Fig. 4 (a) Formation energies (Ef ), (b) discharge voltages (VE), (c) volume changes (ΔV/V), and (d) step-wise volume change (δV) for crystalline (C)
and amorphous (A) LixAs/NaxAs, as a function of x. The experimental discharge voltage profiles of the LIB (Fig. 2b) and SIB (Fig. 3b) are plotted versus
x in (b).

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Nanoscale
which may be the phases that reflect the experimental
capacities of the LIBs and SIBs (see below). These parameters
are explained as follows.
(1) Ef (Fig. 4a): A more negative value of Ef is equivalent to a
higher thermodynamic stability. As x increases to 3, the stabi-
lities of LixAs and NaxAs continuously increase. The hexagonal
phase Li3As is the most stable alloy, with the lattice constant
of a = 4.29 Å and c = 7.65 Å, which is similar to that of the
reference (JCPDS No. 74-1158, P63/mmc, a = 4.387 Å, c =
7.810 Å). LixAs is appreciably more stable than its NaxAs
counterpart. Recently, a similar calculation on phosphorus
consistently showed that the formation energy is the largest
Published on 12 March 2018. Purchased by bizperu@gmail.com on 22 June 2022.
for x = 3 and the Ef value of Li3P is larger than that of
Na3P.49,50 Although the amorphous phase is less stable than
the crystalline phase, it would be produced due to significant
volume expansion, as we found from the experiment (see the
calculation below). It is noteworthy that the relative stabilities
of the LixAs are marginal when x = 3–5, considering that the
difference in Ef is less than 0.03 eV. Therefore, there is a
certain degree of uncertainty in the maximum Li capacity. In
other words, x can be as large as 5 for the amorphous phase,
because the energy difference is less than the thermal energy
at room temperature.
(2) VE (Fig. 4b): The experimental discharge voltage curve
for the LIB (100th cycle at 0.1C as shown in Fig. 2b) is plotted
as a function of x in order to display the excellent correlation
with the theoretically determined curves (VE). If we employ a
finer non-integer Δx interval in the centered-difference
scheme: VE(LixAs) = μ(Li) − [Etot (Lix+1As) − (Lix−1As)]/2, a
smooth VE curve can be generated that demonstrates a better
fit with the experimental curve. For lithiation, when x = 1–2
the plateau feature is equally observed at discharge voltages of
0.7–0.9 V (experiment) and 0.9–1 V (VE). The calculated
capacity at VE = 0 V corresponds to x = 3.8 and 4.0 in the crys-
talline and amorphous phases, respectively, both of which are
close to the experimental value (x = 3.7): 1360 and 1431 mA h g−1
vs. 1306 mA h g−1. The data in the vicinity of VE = 0 show
that even higher capacities (x = 5 and 6) might be achievable
in the amorphous phases, since their VE values are marginal
(−0.03 V). Considering that the capacity of the amorphous
phase is larger than that of the crystalline phase, there may be
a capacity increase if the crystalline phase becomes amor-
phous. The observed capacity increase during repeated cycling
is rationalized by the progressive amorphization, which could
be supported by XRD and TEM data as discussed above.
In the case of the SIB, the calculation shows that the
maximum capacity, at VE = 0 V, is achieved at x = 3.5 (capacity =
1253 mA h g−1). The experimental discharge voltage curve
(200th cycle at 0.1C as shown in Fig. 3b) is plotted against x,
and shows that the maximum capacity corresponds to x = 2.1
(= 750 mA h g−1), which is lower than the experimental value. A
plateau at x = 1–2 is observed consistently for both the experi-
mental and theoretical voltages of 0.4 and 0.55 V, respectively.
However, the experimental curve shows a steep decrease in
capacity after x = 2, suggesting that further sodiation (x > 2) is
blocked by volume expansion, as explained below.
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(3) Volume expansion ΔV/V (Fig. 4c): During lithiation,
volume expansion increases almost linearly with x, and is
slightly less significant in the amorphous phase. The expan-
sion is about 200% for amorphous Li4As, which is smaller
than that of amorphous Li3P (∼280%) reported by Jung and
Han.49 In the case of sodiation, volume expansion is almost
two times that of lithiation, and the crystalline phase exhibits
a more significant volume expansion than the amorphous
phase. It is interesting to note that a 200% expansion is
achieved at Na2As, which is close to the experimental capacity.
We presume that a lithiation/sodiation step with ΔV/V > 200%
induces significant mechanical pulverization, thus limiting
the capacity of the LIBs or SIBs.
(4) Stepwise volume change δV (Fig. 4d): Each lithiation
step suffers an unfavorable volume contraction (δV < 0) at x =
1–5. The crystalline phase shows the most significant contrac-
tion (−9.89 Å3) at the Li3As + Li → Li4As step, where the
volume difference between the amorphous (A) and crystalline
(C) phases (δV(A) − δV(C)) becomes highly positive (= 7.99 Å3).
In the case of sodiation, the largest contraction (−14.21 Å3)
was observed for the crystalline phase under the stepwise NaAs +
Li → Na2As process; the corresponding volume difference
(2.16 Å3) is again positive. Since a Na ion is larger than a Li ion
(radius = 1.02 Å vs. 0.76 Å), this step occurs at a lower stoichio-
metry. We suppose that it is so difficult to achieve the enor-
mous rearrangement of atoms associated with a large volume
contraction, and thus the amorphization can avoid this large
volume contraction. This can explain why the crystalline phase
becomes amorphous after the discharge. It is interesting to
recall that the experimental discharge capacities correspond to
the products (Li4As and Na2As) of these steps. Therefore, the
value of δV(A) − δV(C) might be used to predict the maximum
capacities of LIBs and SIBs.
Now we summarize the calculation as follows. (1) Although
the crystalline phase is more stable than the amorphous phase,
significant volume expansion would produce the amorphous
phase. The increase in capacity during repeated cycling is ration-
alized by progressive amorphization. (2) The VE curve of LIB is
consistent with the experimental data, showing the production
of Li4As (1431 mA h g−1), which is larger than that of Li3As
(1072 mA h g−1), that has generally been accepted until now. The
VE curve of SIB predicts a capacity of 1253 mA h g−1 (Na3.5As),
which is higher than the experimental value (750 mA h g−1).
(3) The volume expansion could be used to predict the experi-
mental capacity of LIB and SIB. The discrepancy in the capacity
of the SIB might originate from mechanical pulverization of the
electrode due to a large volume expansion. The C support of As/
C helps to activate the lithiation of As and so enhance the
capacity close to the calculated values.
4. Conclusion
We synthesized As/C nanocomposites via the ball milling of As
and graphite, and investigated their electrochemical properties
as anode materials for LIBs and SIBs. The As/C exhibited excel-
Nanoscale, 2018, 10, 7047–7057 | 7055

Paper
lent cycling performance in a LIB; the reversible capacity was
1306 mA h g−1 (at 0.1C) after 100 cycles, with a high coulombic
efficiency of 98.3%. The capacities measured at 1C and 2C
were 770 and 786 mA h g−1 after 200 cycles, respectively. The
LIB cell exhibited an increase in capacity upon cycling; a 15%
increase was observed over 5–100 cycles at 0.1C. In the SIB, the
reversible capacity was 750 mA h g−1 (at 0.1C) after 200 cycles,
with a high coulombic efficiency of about 99.3%. As the C rate
reaches 2C, the capacity measured was 645 mA h g−1. Both
LIBs and SIBs exhibit outstanding rate capabilities up to 5C.
First-principles calculations were performed using a sophis-
ticated structure prediction method for crystalline LixAs and
Published on 12 March 2018. Purchased by bizperu@gmail.com on 22 June 2022.
NaxAs (x = 1–6) phases as well as ab initio molecular dynamics
simulations for the amorphous phases. The calculations
predict that curves of discharge voltage versus capacity are in
good agreement with the experimental LIB data; the experi-
mental and theoretical capacities correspond to Li4As, which
is about 4/3 times higher in Li content than Li3As, which has
generally been accepted until now. The theoretical capacity of
SIB corresponds to Na3.5As, which is higher in Na content than
the experimental capacity (Na2.1As). From the volume-expan-
sion analyses, we suggest that the discrepancy in the capacity
of SIB might originate from mechanical pulverization of the
electrode due to a large volume expansion. Indeed, the amor-
phous phase exhibits a higher capacity than the crystalline
phase. Therefore, we suggest that the capacity increase during
repeated cycling is rationalized by the progressive amorphiza-
tion. Furthermore, the C support activates effectively the As
nanoparticles, which can increase the capacity close to the cal-
culated value. Finally, the present study reveals that As is a
promising candidate for applications in high-performance
LIBs and SIBs.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This study was supported by 2014R1A6A1030732,
2017K000494, and 2015R1D1A1A01057606, funded by the
Ministry of Science, and the KIST Institutional Program
(2E27061) and a Korea Institute of Energy Technology
Evaluation and Planning (KETEP) (20162010103990) grant
funded by the Korean Ministry of Trade, Industry and Energy.
This work was also supported by the National Institute of
Supercomputing and Network/Korea Institute of Science and
Technology Information with supercomputing resources
including technical support (KSC-2017-C3-0036). We would
also like to thank Jeonju University for partial financial
support. The HVEM measurements were performed at the
KBSI. The experiments at the PLS were partially supported by
MOST and POSTECH. This research was supported by the
Korea Basic Science Institute under the R&D programme
7056 | Nanoscale, 2018, 10, 7047–7057
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(Project No. D37700) supervised by the Ministry of Science,
ICT and Future Planning.
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