A1302 Journal of The Electrochemical Society, 161 (9) A1302-A1305 (2014)

0013-4651/2014/161(9)/A1302/4/$31.00 © The Electrochemical Society

Lithium Intercalation and Crystal Chemistry of Li3 VO4

Synthesized by Ultrasonic Nebulization as a New Anode Material
for Secondary Lithium Batteries
Won-Tae Kim,a Bong-Ki Min,b Hyun Chul Choi,c Yong Joong Lee,d and Yeon Uk Jeonga,z
a School of Materials Science and Engineering, Kyungpook National University, Daegu 702-701, Korea
b Center for Research Facilities, Yeungnam University, Gyeongsan 712-749, Korea
c Department of Chemistry, Chonnam National University, Gwangju 500-757, Korea
d School of Mechanical Engineering, Kyungpook National University, Daegu 702-701, Korea

Li3 VO4 synthesized by ultrasonic spray pyrolysis was studied as a new anode material for lithium-ion batteries. Li3 VO4 sample
heated up to 500◦ C has a round shape and smaller size compared with the samples synthesized by the solid-state reaction and
solution-based precipitation. Compared to previously reported results, enhanced capacities and rate capabilities were obtained.
Charge and discharge capacities of 250 mAh g−1 after 100th cycle and excellent cyclabililties were observed. The average potentials
for the charge and discharge curves are found to be lower than those of Li4 Ti5 O12 . New crystallographic planes that appear after the
lithiation were identified by XRD and T.E.M. studies.
© 2014 The Electrochemical Society. [DOI: 10.1149/2.0651409jes] All rights reserved.

Manuscript submitted January 28, 2014; revised manuscript received May 27, 2014. Published June 11, 2014.

Carbon-based materials have been widely used for anode materials
of lithium-ion batteries. In an attempt to seek new alternative materi-
als, oxide-based materials have recently received a lot of attention.1
Representative oxide anode is a spinel structure of Li4 Ti5 O12 , which
intercalate three lithium ions per formula at a potential of ∼1.5 V
vs. Li. Reversible intercalation close to the theoretical capacity
(175 mAh/g) and zero strain during the repetitive cycling were
reported.2–6 However, the main drawbacks include a limited capacity
as well as a relatively high potential for an anode material.
Recently, the intercalation properties of layered Li1+x V1-x O2 (R-
3m) anode were reported.7–11 Li1+x V1-x O2 (0.075 ≤ x ≤ 0.1) anode
exhibits very high initial capacities in the low potential region (0.5–
0.01 V vs. Li), and the intercalation mechanism was proposed.10 The
major problem of the fast deterioration due to the breakage of particles
was improved by iron doping in the compound.11 Intercalation prop-
erties of Li2-x VO3 12 for cathode and Li3 VO4 13,14 for anode have been
reported more recently and are still subjects for on-going research.
Details of the reaction mechanism and crystal chemistry of lithiated
Li3 VO4 have not been reported yet.
In the past, Li3 VO4 have been studied for the solid electrolyte,15,16
nonlinear optical materials,17 synthesis,18 and crystal chemistry.18,19
Our group have recently reported electrochemical properties of
Li3 VO4 anodes synthesized by the solid-state reaction and solution-
based precipitation. Because the particle size and shape are mainly
affected by the reaction temperature of the solid-state reaction, it
is not easy to control the size and morphology of the final prod-
ucts. Although smaller and homogeneous particles can be obtained
by solution-based methods, it is hard to avoid the agglomeration of
the primary particles. Ultrasonic spray pyrolysis offers many advan-
tages such as chemical flexibility, inexpensive continuous synthesis,
round shape particles with smooth surface as well as little to no ag-
glomeration of synthesized nano-meter-sized particles, etc.20 We have
successfully synthesized sub-micron sized spherical particles by ultra-
sonic nebulization and report their electrochemical properties, crystal
chemistry, and electronic structure for the lithiated phase of Li3 VO4 .
Experimental
Li3 VO4 samples are synthesized by ultrasonic spray pyrolysis.
500 mL of 1 M vanadate solution were prepared by dissolving V2 O5
in LiOH aqueous solution. Li/V ratio was adjusted at 3.04. The pre-
pared solution was atomized by the ultrasonic nebulizer in an oxygen
atmosphere. The generated mist was continuously heated in a vertical
tube furnace at 800◦ C. Obtained products were heated again at various
z
E-mail: jeong@knu.ac.kr
temperatures in air for 5 hours to control the crystallinity and the level
of moisture content.
X-ray powder diffraction (Cu Kα) is carried out to identify the
phase and to determine the lattice constants. In order to investigate
the charged electrodes, coin cells are dissembled and the removed
electrodes are washed with DMC. Scanning electron microscope (FE-
SEM, HITACHI S-4200) is used to observe the size and morphology
of the powder sample. Selected area electron diffraction (SAED) pat-
terns were obtained to identify the crystal structure in the lithiated
phase by T.E.M. (Tecnai G2 F20, FEI) operated at 200 kV. XPS anal-
ysis was conducted using a VG multilab 2000 spectrometer (Ther-
moVG scientific) in an ultra-high vacuum, which system uses an un-
monochromatized Mg Kα (1253.6 eV) source and a spherical section
analyzer. The spectrum deconvolution was carried out by the PeakFit
program using a Voigt profiles.
The electrochemical properties were evaluated by using 2032-
type coin cells. The slurries for the anode were prepared by mixing of
80 wt% anode material, 10 wt% Super P carbon as a conducting
additive, 10 wt% polyvinylidene fluoride (PVDF) as a binder, and
N-methyl pyrrolidone (NMP) as a solvent. Dispersed slurries were
coated onto a 10 μm thick copper foil followed by drying in an oven
at 120◦ C and cold pressing. For electrolytes, 1 M LiPF6 was dissolved
in the mixed solution of ethylene carbonate (EC) and ethyl methyl
carbonate (EMC) with the ratio of 1:2. Lithium metal was used as the
counter electrode and the coin cells were assembled in an Ar-filled
glove box. The charge/discharge tests were performed between 2.0
and 0.1 V. Charge process was carried out by a constant current (0.2
C-rate), followed by a constant voltage (0.05 C-rate cutoff). Discharge
was performed at 0.2, 0.5, and 1.0 C-rates and the current value for
1.0 C-rate is fixed at 100 mA g−1 .
Results and Discussion
In the case of as-prepared sample, the mist generated by the ultra-
sonic nebulizer was heated immediately in the vertical tube furnace
at 800◦ C in an oxygen atmosphere. The products were heated again
at various temperatures in air. Figure 1 shows the XRD results for
samples heated at various temperatures. Although as-prepared and
250◦ C-heated sample have crystalline peaks, better crystallinity has
been obtained from 500◦ C-heated sample. Synthesized Li3 VO4 sam-
ples have a single phase of orthorhombic structure with a space group
of Pnm21 .18,19 As shown in Figure 1, compared to the as-prepared
sample, 500 and 750◦ C heated samples show increased b-axis and
decreased c-axis parameters. The unit cell volumes decrease with the
increase in heating temperature as 500 and 750◦ C samples have the
unit cell volumes of 170.80 and 169.95 Å3 , respectively. S.E.M. im-
ages are shown in Figure 2. The as-prepared sample shows spherical

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 Journal of The Electrochemical Society, 161 (9) A1302-A1305 (2014) A1303

2.25

2.00 1C 0.5C 0.2C

1.75

Potential vs. Li/Li (V)

1.50

+
1.25

1.00

0.75

0.50

0.25

0.00
0 25 50 75 100 125 150 175 200 225 250 275
-1
Specific capacity (mAh g )

Figure 3. Charge-discharge curves of 10th cycle with various C-rates.

be attributed to the smaller particle size and the spherical shape

Figure 1. XRD patterns of the samples with various heating temperatures.
particles with a size ranging from 0.2–2 μm. Particles do not notice-
ably grow in size upon heating up to 500◦ C, and very fine particles
with a size below 100 nm have been partly observed in 500◦ C-heated
sample. 750◦ C-heated sample shows particles with irregular and rect-
angular shapes, and this morphology is similar to previously reported
results from the synthesis by solid-state reaction.14
Charge and discharge profiles of 10th cycle are shown in
Figure 3. Compared to previously reported results from samples syn-
thesized by solid-state reaction and solution-based precipitation, im-
proved capacity as well as rate capability were observed. This can
morphology. The average potentials for the charge and discharge
curves are found to be lower than those of Li4 Ti5 O12 . Figure 4 shows
the cyclability data for various C-rates. Initial charge capacity of
∼400 mAh g−1 corresponds to the insertion of two lithium ions in
Li3 VO4 structure. After the initial instability intercalation reaction was
stabilized and ∼250 mAh g−1 of capacity is observed after 100th cycle.
∼1.25 mol of Li can be reversibly intercalated in Li3 VO4 host.
In order to analyze the oxidation state of V ions in the lithiated
electrode, the lithiated Li3 VO4 electrode was ex-situ studied by XPS
at different Ar+ sputtering time and the results are shown in Table I
and Figure 5. The binding energies (BEs) of the V 2p3/2 core level
emission for Li3 VO4 electrode charged down to 0.1 V were observed
in the range of 511–519 eV. The spectra of electrodes exhibit an
asymmetric feature, indicating that V ions of electrodes possess the
various oxidation states. In order to quantify the possible oxidations
states of V ions, the obtained V 2p3/2 XPS spectra were curve-fitted
by Voigt profiles. The fitting results are summarized in Table I. Based
on the reported BE values,21,22 we deduce that the oxidation state of V
ions in the lithiated Li3 VO4 electrodes consist of V5+ , V4+ , V3+ , and
V2+ ions. In addition, the atomic% of electrodes shows no noticeable
variation at different Ar+ sputtering time.

450
0.2C charge
400 0.2C discharge
0.2C charge
350 0.5C discharge
Specific capacity (mAh g )

0.2C charge
-1

1.0C discharge
300

250

200

150

100

50

0
0 20 40 60 80 100
Cycle number
Figure 2. S.E.M. images of the samples after (a) as-prepared, (b) heating at
250◦ C, (c) heating at 500◦ C, and (d) heating at 750◦ C. Figure 4. Cyclability data of Li3 VO4 anode with various C-rates.

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 A1304 Journal of The Electrochemical Society, 161 (9) A1302-A1305 (2014)

Table I. Assignments and atomic% of the lithiated Li3 VO4 at different Ar+ sputtering time.

V5+ V4+ V3+ V2+

BE (eV) FWHM (eV) At.% BE (eV) FWHM (eV) At.% BE (eV) FWHM (eV) At.% BE (eV) FWHM (eV) At.%
0 min 517.2 1.6 29.1 516.1 1.6 17.4 514.7 1.6 15.0 513.5 1.6 38.5
1 min 517.2 1.6 26.8 515.8 1.6 20.6 514.3 1.6 14.3 513 1.6 38.3
2 min 517.2 1.6 24.1 515.4 1.6 21.7 514 1.6 17.4 512.8 1.6 36.8
Normalized intensity (arb. units)

V 2p XPS 0.1V 2 min (a) (b)

0.1V 1 min

0.1V 0 min

518 516 514 512

Binding Energy (eV)

Figure 5. XPS spectra with various Ar+ sputtering time for 0.1 V charged
electrode.

In order to study Li insertion sites in the Li3 VO4 structure, XRD

measurement has been carried out with the electrodes of charged at Figure 7. T.E.M. images and electron diffraction results (a) and (c) 500◦ C
0.1 V and discharged at 2.0 V. The results are shown in Figure 6. -heated sample, (b) and (d) 500◦ C -heated sample after charged at 0.1 V.
It is reported that Li3 VO4 has a structure with corner-shared VO4
and LiO4 tetrahedrons and this open structure behaves as a lithium
intercalation host.14 As a result of the insertion of additional lithium the SEI layer can be oxidized when the electrodes are exposed in air.
ions in the empty sites of Li3 VO4 structure, new peaks can appear In order to confirm the new peaks from the charged electrode, T.E.M.
corresponding to the new crystallographic planes. These new observed measurements have been carried out. Selected area electron diffraction
planes have not been reported in the previous research.14–19 New peaks (SAED) data are shown in Figure 7. Each spot pattern corresponds
for the lithiated electrode have appeared at 16.7, 29.6, and 33.0◦ , and to the crystallographic planes, and the intensity of reflection can be
these peaks disappeared in the discharged electrode. These peaks influenced by diffraction conditions as well as the uneven thicknesses
correspond to the new crystallographic planes (001), (020), and (021) of the samples. Although (001) plane is not shown because it is too
in orthorhombic structure, respectively. A Li2 O peak can be also found close to the transmitted beam, (020) and (021) planes are clearly
at 34.3◦ in the lithiated electrode. It is possible that Li2 O can be formed shown in the electron diffraction pattern.
in the SEI layer on the anode during charging or inorganic phases in

Conclusions
Cu Li2O Li3 VO4 powders are successfully synthesized by the atomization
using an ultrasonic nebulizer followed by heating at 500◦ C. Syn-
st
1 discharged electrode thesized Li3 VO4 samples show spherical sub-micron sized particles
smaller than those previously synthesized by other methods. The av-
erage potentials for the charge and discharge curves are found to be
(021)

lower than those of Li4 Ti5 O12 . Although the initial charge capacity
Intensity (a.u.)

measured to be about 400 mAh g−1 , intercalation reaction was stabi-

st
(020)

1 charged electrode
lized after the initial instability and the capacity of 250 mAh g−1 has
(001)

been observed after 100th cycle. It is found that the reversible inter-
calation is ∼1.25 mol of lithium ions in Li3 VO4 host in the potential
range of 2.0–0.1 V vs. Li. XPS measurements suggest the V ions in
As-pressed electrode
the electrodes charged at 0.1 V have multi-valence states. The planes
(200)

for the new peaks in the XRD pattern of lithiated phase were identified
(110)

(002)
(101)
(011)

by T.E.M. study.
(111)

(320)
(112)

(322)
(230)
(201)

(130)
(221)
(100)

(311)

(203)
(141)
(211)

Acknowledgments
10 20 30 40 50 60 70 80 This work is supported by the Ministry of Knowledge Economy
Cu K 2 (degree) and KETEP (Korea Institute of Energy Technology Evaluation and
Planning) for the development of materials and module of kWh-grade
Figure 6. XRD patterns of as-pressed, charged, and discharged electrodes. energy storage for the next generation.

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 Journal of The Electrochemical Society, 161 (9) A1302-A1305 (2014)
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