Journal of Alloys and Compounds 478 (2009) 604–607

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Journal of Alloys and Compounds

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

Sol–gel preparation and electrochemical properties of Na3 V2 (PO4 )2 F3 /C

composite cathode material for lithium ion batteries
Tao Jiang, Gang Chen, Ang Li, Chunzhong Wang, Yingjin Wei ∗
College of Materials Science and Engineering, Jilin University, Changchun 130023, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A Na3 V2 (PO4 )2 F3 cathode material for lithium ion batteries was prepared by using a sol–gel method to
Received 3 September 2008 prepare precursor, and then heat treated the precursor at 650 ◦ C based on TG analysis. Transmission
Received in revised form electron microscopy showed that the material had a small particle size about 20 nm. The Na3 V2 (PO4 )2 F3
15 November 2008
particles were embedded in a network of residual carbon. The content of residual carbon was determined
Accepted 21 November 2008
to be 8.5 wt.%. This residual carbon enhanced the electronic conductivity of the material, which was
Available online 7 December 2008
measured to be 1.0 × 10−3 S cm−1 . The electrochemical insertion mechanism of Na3 V2 (PO4 )2 F3 gradually
shifted from a predominant Na+ insertion to a Li+ insertion in the initial 10 cycles. The material showed a
Keywords:
Lithium ion battery
reversible discharge capacity of 117 mAh g−1 , with quite good capacity retention. The good electrochemical
Cathode material performance of Na3 V2 (PO4 )2 F3 was attributed to its NASICON-type structure, which provided a large ion
Na3 V2 (PO4 )2 F3 diffusion coefficient about 7.2 × 10−10 cm2 s−1 . The good electrochemical performance of Na3 V2 (PO4 )2 F3
Sol–gel method provides an example to use sodium-based materials directly as cathode materials for lithium ion batteries.
Electrochemical property © 2008 Elsevier B.V. All rights reserved.

1. Introduction
The industry of lithium ion batteries has developed rapidly since
their first commercialization in 1991. Lithium ion batteries have
been intensively used in various kinds of portable electronics. They
are also considered as important energy storage devices for future
hybrid electric vehicles. The conventional lithium ion batteries are
normally fabricated using a lithium-based cathode material (such
as LiCoO2 ) and a carbon-based anode material, separated by a non-
aqueous liquid electrolyte. It is no doubt that the need for lithium
ion batteries will increase rapidly once their using performance has
a breakthrough. This will lead to a rapid increase in the consumption
of raw materials, not only transitional elements (such as Co and Fe)
but also lithium itself. A recent study has estimated that the terres-
trial reserves of lithium could be rapidly depleted, considering that
large-scale lithium ion batteries require 100–500 times the amount
of lithium as portable devices use in the near future [1]. The issue is
not insufficient lithium on a global scale, but what fraction can be
used and still be economically effective. Therefore, seeking for new
cathode materials to reduce the over-lean of mineral resources has
been an important task to material scientists.
In the quest for new cathode materials, some sodium-based
cathode materials have recently emerged as a new choice.
A series of sodium fluorophosphates, for example, Na2 FePO4 F
∗ Corresponding author. Tel.: +86 431 85155126; fax: +86 431 85168446.
E-mail address: yjwei@jlu.edu.cn (Y. Wei).
[1], Na3 V2 (PO4 )2 F3 [2–4] and NaVPO4 F [5,6] have shown to
be promising candidates for consideration. Recent works have
demonstrated that these cathode materials exhibit similar elec-
trochemical behaviors to conventional lithium-based cathode
materials. When using them to fabricate lithium ion batteries,
such as a Na3 V2 (PO4 )2 F3 /LiPF6 /Li cell, sodium ions are irreversibly
extracted from the fluorophosphates in the initial charge/discharge
cycles, while the subsequent cycles are dominated by reversible Li+
extraction/insertion [3].
Sodium vanadium fluorophosphates, Na3 V2 (PO4 )2 F3 , was firstly
prepared by Meins in 1999 [7]. Na3 V2 (PO4 )2 F3 has a tetragonal
crystal structure with space group of P42 /mnm. This structure is
characterized by an extended three-dimensional framework built
up from [V2 O8 F3 ] bi-octahedral and [PO4 ] tetrahedral. The [V2 O8 F3 ]
bi-octahedral is bridged by one fluorine atom, while the sodium
ions are statistically distributed in the resultant network. This
NASICON-type structure is expected to facile fast ion diffusion.
However, as many of phosphate cathode materials, Na3 V2 (PO4 )2 F3
has shown a low electronic conductivity due to the separation of
vanadium atoms by [PO4 ] tetrahedral. Preparation of carbon con-
tained phosphate cathode materials has been an effective way to
improve the electronic conductivities of these materials. Barker et
al. have prepared Na3 V2 (PO4 )2 F3 using a two-step process involving
the orthorhombic V(III) phosphate, VPO4 , as the reaction inter-
mediate [4]. This method requires a complex operation procedure
and a long processing time. Moreover, the structure and morphol-
ogy of VPO4 intermediate are important for the electrochemical
properties of the final product. In this study, we introduced a sim-

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 T. Jiang et al. / Journal of Alloys and Compounds 478 (2009) 604–607 605

Fig. 2. X-ray diffraction pattern of the Na3 V2 (PO4 )2 F3 /C composite material.

Fig. 1. TG curve of the precursor material.

residual water. With the further heating, a big weight loss about 18%
ple sol–gel process to prepare Na3 V2 (PO4 )2 F3 /carbon composite appears between 160 and 270 ◦ C, which is assigned to the decom-
cathode material. The material prepared by this method showed position of NH4 VO3 and NH4 H2 PO4 . The third weight loss about
promising electrochemical performance and could be considered 12% appears between 270 and 600 ◦ C. This can be attributed to the
as a cathode material for lithium ion batteries. release of carbon oxides arising from the pyrolysis of citric acid. No
significant weight loss is observed above 600 ◦ C. Therefore, a heat-
2. Experimental ing temperature of 650 ◦ C used in this experiment is proper for the
preparation of Na3 V2 (PO4 )2 F3 .
Na3 V2 (PO4 )2 F3 was prepared using NH4 VO3 , NaF and NH4 H2 PO4 as the starting
materials. Citric acid (C6 H8 O7 ) was employed as both a chelating species and a carbon Fig. 2 shows the XRD pattern of the as-prepared Na3 V2 (PO4 )2 F3
source, which would reduce the V5+ ions to V3+ . For the first step, NaF, NH4 VO3 and material. All of the diffraction peaks can be indexed well to the
NH4 H2 PO4 powders were dissolved in deionized water with a stoichiometric ratio. single phase of Na3 V2 (PO4 )2 F3 with a tetragonal structure. This
A saturated citric acid solution was then titrated to the above solution. The molar
result is in good agreement with previous reports [4]. The weak
ratio of citric acid with respect to vanadium ions in the solution was 0.8. This solution
was constantly stirred at 80 ◦ C to form a uniform sol, followed by drying at 120 ◦ C to
and broad diffraction peaks indicates a small coherent domain size
obtain a gel precursor. This gel precursor was pre-treated at 300 ◦ C in N2 atmosphere of the material. The average coherent domain size is estimated to be
for 4 h. The resultant powder was then pressed into a tablet and heat treated again 15 nm according to the Deby–Scherrer method. Even some residual
at 650 ◦ C for 8 h in N2 atmosphere. The product was removed from the furnace after carbon was observed in the material according to the following TEM
cooling to room temperature.
experiment; there are no traces of carbon in the XRD pattern. This
Thermogravimetric (TG) analysis on the precursor material was performed on
an SDTA851E thermoanalyzer under N2 flow. The measurement was performed implies that the residual carbon in the material is in an amorphous
between room temperature and 850 ◦ C at a heating rate of 10 ◦ C/min. The crystal state.
structure of the material was studied by X-ray diffraction on a Rigaku AXS D8 diffrac- The morphology of the material was studied by TEM as shown
tometer with Cu K␣ radiation. The diffraction data was recorded in the 2 range of
in Fig. 3. The material is composed of small dark particles which are
10–80◦ with a scan rate of 3◦ /min. The morphology of the material was studied by
transmission electron microscopy (TEM, Hitachi H-8100IV). For electronic conduc-
embedded in a light grey network. The dark region corresponds to
tivity measurement, the sample was pressed into a tablet with diameter of 8 mm the Na3 V2 (PO4 )2 F3 particles. The average particle size is estimated
and thickness of 2 mm under 15 MPa, followed by heat treatment at 200 ◦ C for 1 h. to be 20 nm, which fits well to that of XRD analysis. The light grey
Both surfaces of the tablet were covered by silver paste. The electronic conductivity region can be identified as the residual carbon in the sample. The
measurement was performed on a Keithley 2400 Source Meter by the van der Pauw
content of residual carbon was measured to be 8.5 wt.% from gravi-
method [8].
The electrochemical experiment was carried out using a coin battery cell. A metric analysis after dissolution of the material in a hydrochloric
metallic lithium foil served as the anode electrode. The cathode electrode was fabri- solution. The residual carbon prevents the growth of Na3 V2 (PO4 )2 F3
cated by blending the Na3 V2 (PO4 )2 F3 active material (75 wt.%) with acetylene black
conductive additive (10 wt.%) and poly-vinylidenefluoride binder (PVDF, 15 wt.%)
dissolved in N-methyl-2-pyrrolidone (NMP). The slurry was pasted on an Al foil
and then dried at 100 ◦ C in a vacuum oven for 12 h. The electrode was 8 mm × 8 mm
in size and loaded about 3 mg of active material. The cathode and anode electrodes
were separated by Celgard 2400 membranes. The electrolyte was a 1-mol L−1 lithium
hexafluorophosphate (LiPF6 ) dissolved in ethylene carbonate (EC) and dimethyl
carbonate (DMC) (EC:DMC = 1:1, by v/v ratio). The charge/discharge cycling was per-
formed on a Land® battery tester. In order to study the electrochemical insertion
mechanism of Na3 V2 (PO4 )2 F3 , the battery was disassembled after certain cycles.
The Li/V molar ratio of the cathode electrode was analyzed by Inductively Cou-
pled Plasma-Atomic Emission Spectroscopy (PE® , ICP-AES/1000). Electrochemical
impedance spectroscopy (EIS) was studied by a ZAHNER® -IM6e electrochemical
workstation. The impedance spectra were recorded using an AC voltage of 5 mV
in the frequency range from 1 MHz to 1 mHz.

3. Results and discussion

Fig. 1 shows the TG curve of the precursor material. The ini-

tial slight weight loss about 2% is attributed to the evaporation of Fig. 3. TEM image of the Na3 V2 (PO4 )2 F3 /C composite material.
606 T. Jiang et al. / Journal of Alloys and Compounds 478 (2009) 604–607
Fig. 4. Typical charge/discharge potential profiles of the Na3 V2 (PO4 )2 F3 /C composite
material.
particles, which results in a small particle size. On the other hand,
this residual carbon also provides good electronic contact between
Na3 V2 (PO4 )2 F3 particles. As a result, a high electronic conductivity
about 1.0 × 10−3 S cm−1 is obtained for the material.
Galvanostatic charge/discharge cycling of Na3 V2 (PO4 )2 F3 was
carried out in the potential region between 3.0 and 4.5 V. The cell
was cycled with a current density of 13 mA g−1 which corresponds
to a C/10 rate. Fig. 4 shows the typical charge/discharge potential
profiles of the material. The first charge profile can be divided into
two regions, i.e. 3.0–4.0 V and 4.0–4.5 V. Each region has a spe-
cific capacity about 64 mAh g−1 , corresponding to one mol of Na+
ions extracted from the material lattice. It is known that there are
three different Na positions in the Na3 V2 (PO4 )2 F3 structure. There-
fore, the above potential regions correspond to Na+ extraction from
two different crystallographic sites, respectively. The total charge
capacity for the 1st cycle is 127 mAh g−1 , which is very close to the
theoretical capacity (128 mAh g−1 ) of Na3 V2 (PO4 )2 F3 in this poten-
tial region. The subsequent discharge process displays a very similar
potential profile to the first charge, which indicates good electro-
chemical reversibility of the material.
Fig. 5 plots the discharge capacities vs. cycle numbers of the
Na3 V2 (PO4 )2 F3 material. The material exhibits a reversible dis-
charge capacity of 117 mAh g−1 in the 1st cycle, with quite good
capacity retention in the following cycles. The potential profiles of
the 5th and 10th cycles exhibit very similar shape to that of the 1st
cycle. As shown below, the electrochemical insertion mechanism
of Na3 V2 (PO4 )2 F3 will transform gradually from Na+ insertion to
Li+ insertion during the initial several cycles. The similar potential
profiles during the whole cycling indicate that Li+ ions replace Na+
ions at the same crystallographic sites, and this replacement does
not cause significant changes to the material structure.
In order to investigate the electrochemical insertion mechanism
of Na3 V2 (PO4 )2 F3 , ICP analysis was carried out to measure the Li/V
molar ratio of the cathode material after certain cycles. The results
are summarized in Table 1. It is definite that two moles of Na+ were
extracted from Na3 V2 (PO4 )2 F3 after the first charge. Therefore, the
Li/V ratio at the end of first charge should be zero, which is con-
Table 1
Li/V molar ratio in the Na3 V2 (PO4 )2 F3 /C composite material upon different charge/discharge cycles.
4.5 V at the first charge 4.0 V at the first discharge
Estimated value 0 0.5
Experimental value 0 0.38
Fig. 5. Discharge capacities vs. cycle numbers of the Na3 V2 (PO4 )2 F3 /C composite
material.
Table 2
SEI resistance (Rf ), charge transfer resistance (Rct ) and ion diffusion coefficient of the
Na3 V2 (PO4 )2 F3 /C composite material upon different charge/discharge cycles.
Cycle no. Rf () Rct () D (cm2 s−1 )
1 502 44 6.6 × 10−10
10 548 112 7.2 × 10−10
30 590 615 2.0 × 10−10
firmed by the experimental value listed in Table 1. Subsequently,
when the cell was discharged to 4.0 V, one would obtain a Li/V ratio
of 0.5 if the insertion mechanism was dominated by Li+ . This corre-
sponds to a chemical composition of NaLiV2 (PO4 )2 F3 of the cathode
material. However, we obtained an experimental value of 0.38. This
implies that a Li+ /Na+ mix-insertion mechanism took place dur-
ing the first discharge. Similarly, a Li/V ratio of 0.69 was obtained
instead of the estimated value of 1 at the end of first discharge. With
the further cycling, a Li/V ratio of 0.97 was obtained at the end of
10th cycle, which is very close to the estimated value. Based on
this, it can be concluded that there is a gradual shift in the insertion
mechanism from predominant Na+ insertion to Li+ insertion. Two
possible reasons are supposed to explain this insertion mechanism.
Firstly, Li+ has a smaller ionic radius than that of Na+ . Therefore,
they are much easier to insert into the material framework than
Na+ ions. On the other hand, unlike Li+ ions, the bigger Na+ ions
cannot penetrate the solid electrolyte interfacial (SEI) film on the
cathode material once it has formed in the initial cycles.
Electrochemical impedance spectroscopy was carried out after 1,
10 and 30 cycles. The corresponding Nyquist plots are given in Fig. 6.
The very small intercept at the Zreal axis is attributed to the internal
resistance of the battery cell. The semi-circle in the high frequency
region is due to the resistance of SEI film (Rf ); while the other one in
the middle frequency region is due to the charge transfer resistance
(Rct ). The sloping line in the low frequency region corresponds to
the diffusion of Li+ /Na+ ions in the electrode bulk, namely the War-
burg impedance. The SEI resistance and charge transfer resistance
after 1, 10 and 30 cycles are obtained by fitting the Nyquist plots
using the ZView package. The results are listed in Table 2. It is seen
3.0 V at the first discharge 3.0 V at the 10th discharge
1 1
0.69 0.97
 T. Jiang et al. / Journal of Alloys and Compounds 478 (2009) 604–607
Fig. 6. Nyquist plots of the Na3 V2 (PO4 )2 F3 /C composite material after 1, 10 and 30
cycles.
Fig. 7. Linear fitting of Zreal vs. ω−1/2 after 1, 10 and 30 cycles.
from the table that the SEI film has basically formed during the 1st
cycle and changes very little during following cycles. In contrast, the
charge transfer resistance is strongly influenced by cycling. During
the 1st 10 cycles, the charge transfer resistance increased from 44
to 112 , and then increased prominently to 615  after 30 cycles.
This should be responsible for the relatively fast capacity fading
of the material after 10 cycles. Actually, the capacity fading rate is
0.12 mAh g−1 per cycle in the initial 10 cycles, which increases to
0.28 mAh g−1 per cycle in the following cycles.
The ion diffusion coefficient of the material after different cycles
can be evaluated by the following equation [9]:
R2 T 2
D=
2S 2 n4 F 4 C 2  2
here R is the gas constant, T the absolute temperature, S the surface
area of the cathode electrode, n the number of electrons involved in
reaction (n = 1), F the Faraday constant, and  is the Warburg factor
which obeys the following relationship:
Zreal = Rf + Rct + ω−1/2
Fig. 7 displays the linear fitting of Zreal vs. ω−1/2 , from which the
slope  can be obtained. Using this value the ion diffusion coeffi-
607
cient of the material was calculated and listed in Table 2. The results
show that the ion diffusion coefficient of Na3 V2 (PO4 )2 F3 is between
2.0 × 10−10 and 7.2 × 10−10 cm2 s−1 in the whole cycling. The diffu-
sion coefficient slightly increased in the 1st 10 cycles. This indicates
the gradual change of the insertion mechanism from Na+ insertion
to Li+ insertion because Li+ ions have a smaller ionic radius and
mass than that of Na+ ions which resulted in a faster ion mobil-
ity. On the other hand, the decrease of diffusion coefficient after
10 cycles was probably related with the changes in microstruc-
tures of the electrode materials with charge–discharge cycling.
The ion diffusion coefficient of Na3 V2 (PO4 )2 F3 is much larger than
that of olivine LiFePO4 . The later has been reported a value about
1.8 × 10−14 cm2 s−1 [10]. The different ion diffusion coefficients
between both phosphate materials are related to their structural
properties. As for olivine LiFePO4 , Li+ ions can only transport in a
one-dimensional pathway. While the NASICON-type structure of
Na3 V2 (PO4 )2 F3 allows Li+ or Na+ ions transport in a much opening
framework, which results in a large ion diffusivity.
4. Conclusions
A Na3 V2 (PO4 )2 F3 /C composite cathode material has been pre-
pared by a sol–gel method. Citric acid played not only a chelating
species but also a carbon source in the preparation. An excessive cit-
ric acid produced some residual carbon in the material. This residual
carbon prevented the growth of Na3 V2 (PO4 )2 F3 particles. On the
other hand, the residual carbon provided good electronic contact
between material particles, leading to a high electronic conductiv-
ity as 1.0 × 10−3 S cm−1 . The electrochemical insertion mechanism
of Na3 V2 (PO4 )2 F3 gradually shifted from predominant Na+ inser-
tion to Li+ insertion in the initial cycles. The material showed
a reversible discharge capacity of 117 mAh g−1 , with quite good
capacity retention. The good electrochemical performance of the
material was benefited from its NASICON-type structure, which
allows fast ion diffusion. Therefore, Na3 V2 (PO4 )2 F3 can be con-
sidered as a potential cathode material for lithium ion batteries.
The use of such sodium-based cathode materials is competitive for
industrial purpose because the materials can be prepared at much
lower cost than any lithium analogue.
Acknowledgements
This work was supported by Major State Basic Research Program
under grant nos. 2007CB216406 and 2009CB220100. The authors
thank the Program for Changjiang Scholar and Innovative Research
Team in University (No. IRT0625) and the Program for New Century
Excellent Talents for financial supporting.
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