Materials Research Bulletin 39 (2004) 1803–1810

www.elsevier.com/locate/matresbu

Synthesis of LiFePO4 with fine particle

by co-precipitation method
K.S. Parka,*, K.T. Kangb, S.B. Leeb, G.Y. Kimb, Y.J. Parkc, H.G. Kimb
a
Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA
b
Department of Materials Science and Engineering, KAIST, Daejeon 305-701, South Korea
c
Battery Technology Team, ETRI, Daejon 305-350, South Korea

Received 12 February 2004; received in revised form 11 June 2004; accepted 7 July 2004

Abstract

LiFePO4 is a potential candidate for the cathode material of the lithium secondary batteries. A co-precipitation
method was adopted to prepare LiFePO4 because it is simple and cheap. Nitrogen gas was needed to prevent
oxidation of Fe2+ in the aqueous solution. The co-precipitated precursor shows the high reactivity with the reductive
gas, and the single phase of LiFePO4 is successfully synthesized with the aid of carbon under less reductive
conditions. LiFePO4 fine powder prepared by co-precipitation method shows high rate capability, impressive
specific capacity and cycle property.
# 2004 Elsevier Ltd. All rights reserved.
Keywords: A. inorganic compounds; B. electrochemical measurements; C. X-ray diffraction; D. XAFS (EXAFS and XANES)

1. Introduction

The layered LiCoO2 is one of the earliest developed cathode materials, and the good performance and
the stability makes it the main commercially used cathode material despite its toxicity and high cost.
Therefore, alternative cathode materials have been pursued to improve the battery performances and cut
down the cost. Among the several cathode materials, LiFePO4 of the phospho-olivine family proposed by
Goodenough group appears particularly interesting due to low cost and environmental compatibility [1].
For LiFePO4, the discharge voltage is about 3.4 V versus Li/Li+ and the capacity fade is small even after

* Corresponding author.
E-mail address: gappa37@dreamwiz.com (K.S. Park).

0025-5408/$ – see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2004.07.003
1804 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810

several hundred cycles. Its reversible capacity is about 140–150 mAh/g, which is as large as that of
present cathode materials. Owing to the impressive electrochemical properties of the polyanion-
containing minerals like LiFePO4, some researchers have searched a large number of iron-containing
minerals recently [2].
The problem of this material is low electronic conductivity and low lithium diffusivity [3]. The
low conductivity leads to initial capacity loss and poor rate capability. The conductivity problems
have been studied by particle optimizing [4], metal doping [5], and coating with the electronically
conductive materials like carbon, metal and metal oxide [6–8]. Among these approaches, the
optimization of the particle size can be easily achieved by solution methods like co-precipitation,
sol–gel and hydrothermal synthesis [6–12]. Recently, Franger et al. tried a co-precipitation method
to synthesize LiFePO4, but homogeneous powder was not prepared because of the reduction of
phosphate entities into phosphides in the reductive conditions [10]. Arnold et al. also synthesized
LiFePO4 with Li3PO4 as a minor impurity phase by a co-precipitation method [11]. They showed
impressive electrochemical results and reported the effect of various reductive conditions on the phase
homogeneity.
Here, we adopted a co-precipitation method in precursor preparation to obtain fine powders and to
reduce the synthesis time and cost. The carbon black was mixed as a reductive additive to prevent the
oxidation of the iron into 3+ and to improve the electronic conductivity.

2. Experimental

The LiFePO4 cathode material was prepared by a co-precipitation method in de-ionized water at room
temperature. An aqueous solution of (NH4)2Fe(SO4)2
6H2O (99%, Aldrich) and H3PO4 (99.999%,
Aldrich) was added to an aqueous solution of LiOH (98%, Aldrich). A thick mixture of a green-colored
deposit and solution was obtained after stirring for 10 min, blowing nitrogen gas into the solution through
a tube. The deposit was washed with the de-ionized water, separated by a centrifugal separator and dried
in a vacuum oven at 60 8C for 5 h. After drying, the powder was mixed with 3 wt.% high surface area
carbon black and pressed into a disk-shaped pellet. The mixture was annealed from 550 to 800 8C in a
flow of nitrogen gas containing 1 vol.% of hydrogen.
SEM (Philips, XL30S) was used to observe the particle size and morphology, and the particle size
measurement (Cilas, 1064) was also done to determine the particle size and its distribution. X-ray
diffraction (Rigaku, Cu Ka radiation) was used to examine the phase homogeneity. The X-ray absorption
near-edge structure (XANES) measurement was carried out to confirm the iron oxidation state. Fe
K-edge X-ray absorption spectra have been recorded on the BL3C1 beam line of Pohang Light Source
(PLS). A Si double crystal monochromator has been used with detuning to about 80% in intensity to
eliminate higher order harmonics. The data have been collected in transmission mode with the nitrogen
gas-filled ionization chambers as detectors. The standard LiFePO4 powder for XANES analysis was
prepared at 800 8C by solid-state reaction and its iron oxidation state was confirmed by Mössbauer
spectroscopy [4].
For electrochemical measurements, the LiFePO4/C/PVDF mixture with weight ratio 75/20/5 was used
as the cathode and the electrolyte was 1 M LiClO4 in propylene carbonate (PC). Metallic lithium foil was
used for the counter and reference electrodes. The electrochemical experiment was controlled with an
EG&G 273A system and performed between 2.7 and 4.1 V versus Li/Li+ at room temperature.
 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810 1805

3. Results and discussion

The co-precipitation method was used for preparing the precursor in this work. Blowing nitrogen gas
into the solution was essential at the co-precipitation stage; otherwise oxidation of the Fe2+ into Fe3+
occurred on the aqueous solution surface. A proposed role of nitrogen gas would be to make the nitrogen
bubble on the solution surface, and this reduces the contact area between the solution and the air.
Therefore, by blowing nitrogen gas it could be possible to prevent the oxidation of the Fe2+ and then to
stir the solution vigorously for homogeneous mixing. Arnold et al. also pointed out the need of the inert
atmosphere during the co-precipitation stage and they performed their co-precipitation process under an
inert atmosphere in order to exclude oxygen [11]. But the blowing nitrogen into the aqueous solution is
enough to prevent oxidation of the iron in our experiments.
Fig. 1 shows the X-ray diffraction profiles of LiFePO4 prepared at 550, 600, 700 and 800 8C for 1 h. A
single phase of LiFePO4 is not synthesized from the pure co-precipitated precursor, and the narrow phase
stability window of heating time and the reductive gas flow rate is shown in Fig. 1(a and b). It is hard to
make a single phase of LiFePO4 without Li3PO4 and Li3Fe2(PO4)3, and this might be caused by the high
reactivity of co-precipitated precursor in reducing atmosphere containing the hydrogen gas. So, the
control of the reducing power is needed, and therefore the carbon is introduced to the precursor as a
reducing agent. After adding a small amount of the carbon, a single phase of LiFePO4 with an olivine

Fig. 1. X-ray diffraction profiles of LiFePO4 with various synthesis conditions.

1806 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810

structure could be successfully synthesized under the less reductive annealing conditions as shown in
Fig. 1(c–e). The carbon black is a reductive additive to prevent the oxidation of the Fe2+, and this could be
a solution of the phase purity problem of the co-precipitated LiFePO4 [10,11]. The Li3PO4 phase appears
again above 700 8C as shown in Fig. 1(f) because of the high reducing power by the formation of carbon
monoxide at a higher temperature [13].
The XANES analysis is done in order to identify the iron oxidation state, because Fe3+ phases would
not be detected by X-ray diffraction if the phases were amorphous or nano-particulates [4]. The standard
powder for XANES analysis was prepared at 800 8C following Yamada’s solid-state reaction methods
[4], and its iron oxidation state was confirmed by Mössbauer spectroscopy. The isomer shift, which is
an indicator of the iron oxidation state, has a value of 1.237 mm/s and the quadrupole splitting is
2.9957 mm/s as shown in Fig. 2(a). The Fe3+ doublet is not detected in this case and the isomer shift of

Fig. 2. (a) Mössbauer spectrum of the standard LiFePO4 and (b) XANES spectra of LiFePO4 with various heat treatment
temperatures.
 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810 1807

Fig. 3. SEM images of LiFePO4 annealed at (a) 600 8C and (b) 700 8C for 1 h.

1.237 mm/s indicates the pure Fe2+. The XANES measurement result compared with the standard sample
is given in Fig. 2(b). The position of Fe K-edge is 7127.2 eV at all synthetic temperatures, so the Fe in
LiFePO4 prepared by the co-precipitation method has the oxidation state of 2+.
The particle size of the LiFePO4 annealed at 600 8C for 1 h is very small (<1 mm) as shown in Fig. 3;
and after annealing at 700 8C for 1 h, the particles become larger and sintered. The particle size
measurement in volume distribution mode shows that the D90 values are 14.8 mm at 600 8C and 24.1 mm
at 700 8C. D90 is the particle diameter which has the cumulative value as large as 90%. Therefore, poor
electrochemical properties are expected in case of annealing at 700 8C because of the diffusion limit of
the lithium through the LiFePO4/FePO4 interfaces [1].
Fig. 4 shows the initial voltage profiles of LiFePO4 with the annealing temperature at the rate of C/5.
The electrochemical properties of half-cells were measured at room temperature. LiFePO4 prepared at
550 and 600 8C shows small differences in the charge/discharge properties, but larger over-voltage and
initial capacity loss are observed at the sample prepared at 700 8C. This could be explained by the
sintering effect and larger particle size as pointed out from Fig. 2(b). Particle-size analysis predicted

Fig. 4. Initial voltage profiles of LiFePO4 with various annealing temperature.

1808 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810

Fig. 5. Initial charge capacities of LiFePO4 with various annealing times.

particle agglomerates above 10 mm in size in cases of annealing at 550 and 600 8C, and therefore the
initial capacity loss is still observed even though very small particles are obtained [3]. LiFePO4 prepared
at 600 8C shows the largest specific capacity; it has an initial charge capacity of 110 mAh/g and an initial
discharge capacity of 101 mAh/g.
The annealing time was also varied as a synthetic parameter. The initial discharge capacities with the
various annealing time at the rate of C/5 are summarized in Fig. 5. Annealing at 600 8C for 5 h makes the
largest capacity, 127 mAh/g at the initial charge and 119 mAh/g at the initial discharge, and the capacities
tend to decrease after annealing for 10 h. This phenomenon could be explained by the structural stability
in the reductive conditions. Fig. 6 shows X-ray diffraction profiles with different annealing time. The

Fig. 6. X-ray diffraction profiles of LiFePO4 with different annealing times.

 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810 1809

Fig. 7. SEM image of LiFePO4 annealed at 700 8C for 15 min.

crystallinity gets worse and the unknown impurity phases are present after annealing for 10 h. This may
be because exposure to the reductive atmosphere for more than 5 h could decompose the lattice structure.
A decrease in the annealing time to less than 1 h is effective to increase the capacity in the case of
annealing at 700 8C. Fig. 7 is the SEM image of LiFePO4 annealed at 700 8C for 15 min; it shows that the
short annealing time can reduce the sintering effect. The D90 values in volume distribution mode are
decreased from 24.1 mm at 1 h to 12.5 mm at 15 min as well, and these particle size effects would be the
reason for increasing the capacity because of poor conductivity of LiFePO4.
LiFePO4 prepared at 600 8C for 5 h shows relatively stable charge/discharge cycle property as shown
in Fig. 8. The initial charge capacity is 132 mAh/g and discharge capacity is 125 mAh/g at the rate of C/
10, and after the initial cycle the capacity is retained with a coulombic efficiency which is about 99%.
Moreover, LiFePO4 prepared by the co-precipitation shows good rate capability, although LiFePO4
generally shows poor rate capability owing to its poor conductivity. The discharge capacity drop when
increasing the current density from C/10 to 1 C is only 13%. This impressive rate capability could be
explained by the very small particle size distribution. The D90 in number is 0.38 mm and the D90 in

Fig. 8. Cycle properties of LiFePO4 after annealing at 600 8C for 5 h.

1810 K.S. Park et al. / Materials Research Bulletin 39 (2004) 1803–1810

volume is 12.2 mm in case of LiFePO4 prepared at 600 8C for 5 h. Therefore, it could be thought that most
particles have very small particle sizes and only a few of them have large particle size in the form of
particle agglomerates. By optimizing the particle size, it is possible to overcome the conductivity
problems [4], and the co-precipitation method would be an alternative way to prepare LiFePO4.

4. Conclusion

The simple co-precipitation method is successfully introduced to prepare LiFePO4 with fine particles.
Nitrogen gas is needed to prevent oxidation of the Fe2+ in the aqueous solution. The co-precipitated
precursor shows the high reactivity with the reductive gas, and the single phase of LiFePO4 is
successfully synthesized with the aid of carbon under less reductive conditions. The carbon is very
useful to control the reducing power and to make single-phase LiFePO4. By changing the heating
temperature and time, it is possible to control the particle size, distribution and crystallinity that affect
the electrochemical properties. The largest discharge capacities of LiFePO4 are 125 mAh/g at the rate of
C/10 and 110 mAh/g at the rate of 1 C after annealing at 600 8C for 5 h, and these values indicate a high
rate capability probably due to the very small particle size.

Acknowledgements

Experiments at PLS were supported in part by MOST and POSTECH.

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