Materials Letters 61 (2007) 1260 1264

www.elsevier.com/locate/matlet

Molten salt synthesis and electrochemical properties of spherical

LiFePO4 particles
Jiang-Feng Ni, Heng-Hui Zhou , Ji-Tao Chen, Xin-Xiang Zhang
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China
Received 23 February 2006; accepted 3 July 2006
Available online 21 July 2006

Abstract

Well-crystallized LiFePO4 was directly synthesized by the KCl molten salt (MS) method. According to this method, the pre-sintered
intermediate was mixed with KCl, and then sintered at a certain temperature, which was determined by thermogravimetric analysis (TGA). The
olivine structure and spherical morphology were confirmed by X-ray diffraction (XRD) and field emission scanning electron microscope (FE-
SEM). The spherical products show a higher tap density, which will benefit the enhancement of volumetric energy density. The electrochemical
behavior was studied by cyclic voltammetry and galvanostatic tests. The LiFePO4 product sintered at 755 C for 3 h exhibits the best
electrochemical performance. At a rate of 0.1 C, it can deliver an initial capacity of 130.3 mAh g 1, and a capacity of 137.2 mAh g 1 at the 40th
cycle. At a high discharge rate of 5 C, it still exhibits a capacity of 92 mAh g 1.
2006 Elsevier B.V. All rights reserved.

Keywords: Lithium iron phosphate; Molten salt; Spherical; Volumetric energy density; Electrochemical performance

1. Introduction been conducted successfully by solid-state reaction, but they

Recently, olivine LiFePO4 is receiving increasing attention
due to its high reversible capacity, low material cost, no toxicity,
and super safety [15]. Although it suffers from poor rate
performance at room temperature associated with extremely
low electronic conductivity, various effective strategies such as
mixing with conductive additives [6], doping with supervalent
metal ions [79], and synthesis of nanoparticles [10] have
greatly alleviated this limitation.
Morphology also addresses a great effect on LiFePO4 prop-
erties and its practical application. Among various materials
with different morphologies, spherical morphology material
shows a great advantage over that of other morphologies. The
advantage includes high tap density, high volumetric energy
density, and high safety associated with low interfacial energy.
As a result, lots of efforts have been devoted to the realization of
spherical LiFePO4 product. For example, Bewlay et al. obtained
LiFePO4 spherical product by spray solution and subsequent
sintering at 800 C [11]. Spherical LiFePO4 products have also
suffer from tough synthesizing condition: high sintering
temperature and long sintering time [3,12].
In recent years, the molten salt method, also known as the
flux method, has been widely explored in the preparation of
electrode materials [13,14]. In comparison with conventional
solid-state reaction, the molten salt method shows accelerated
reaction rate and controllable particle morphology, because the
salt melt exhibits higher ion diffusion rate and strong dissolving
capability [15]. However, to the best of our knowledge, few
reports have focused on the molten salt synthesis of olivine
LiFePO4.
In the present work, we adopted a KCl molten salt (MS)
method to synthesize well-crystallized, spherical LiFePO4
product at a short sintering time. The crystalline and mor-
phologic characteristics were investigated by X-ray diffraction
(XRD) and field emission scanning electron microscope (FE-
SEM). The electrochemical performances were studied by
cyclic voltammetry and galvanostatic tests.
2. Experimental

Corresponding author. Tel./fax: +86 10 62757908. Stoichiometric amounts of Li2CO3, Fe(II)C2O42H2O, and
E-mail address: hhzhou@pku.edu.cn (H.-H. Zhou). NH4H2PO4 were weighed and mixed. A certain amount of
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.07.006
 J.-F. Ni et al. / Materials Letters 61 (2007) 12601264
sucrose (22 g per mol of LiFePO4) as conductive precursor was
added and the final product was expected to contain 3 wt.%
carbon. The mixture was ground by high-energy ballmilling,
and then pre-sintered at 450 C for 5 h. After the pre-sintered
intermediate cooled down, it was mixed with KCl (AR, Beijing
Chemicals) in a molar ratio of 1:2 [13], and reground again, then
sintered at 755 C for 1 h, 3 h, and 6 h, respectively. The
products were washed with de-ionized water and ethyl alcohol,
filtered, and dried in vacuum.
Thermogravimetric analysis was carried out on a simulta-
neous thermal analysis apparatus (SDT 2960, TA Instruments)
to determine the sintering temperature. The mixture was heated
from room temperature to 800 C at a heating rate of 10 C min-
1
. The measurement was performed in nitrogen flow, using -
Al2O3 as the reference material.
XRD patterns of the powder samples were recorded using a
Rigaku Dmax-2400 automatic diffractometer equipped with
CuK radiation ( = 0.15406 nm). FE-SEM (Amray 1910) was
used to observe particle morphology. Prior to observation, the
samples were dispersed in ethanol by ultrasonic processing, and
then dropped on a clean silicon slice.
Cyclic voltammetry was carried out using a powder micro-
electrode technique [9]. The electrochemical response was
measured on a CHI660B electrochemical working station at a
scanning rate of 0.1 mV s 1.
The charge and discharge behavior was performed on a
Wuhan Lisun battery program-controlled test system. The
electrode mixture consists of LiFePO4, acetylene black and
polytetrafluoroethylene (PTFE) in a ratio of 80:15:5. The details
of battery manufacture have been described in a previous work
[9].
3. Results and discussion
Fig. 1(a) presents the TG-DTA curves of the conventional solid-
state reaction to prepare LiFePO4. It is found that there are three weight
loss processes, which are all presented below 420 C and due to the
decomposition of raw materials [16]. The weight loss in the range of
210230 C, differing from the TG curve of mixture without
Fig. 1. TG-DTA curves of (a) the raw materials and (b) the mixture of
intermediate and molten salt KCl.
1261
Fig. 2. X-ray diffraction patterns of the LiFePO4 samples prepared at 755 C for
different times.
conductive additive [16], is due to the degradation of sucrose. The
LiFePO4 formation reaction can be described as follows:
1=2Li2 CO3 FeIIC2 O4 d2H2 O NH4 H2 PO4 LiFePO4
3=2CO2 CO 7=2H2 O NH3
Fig. 1(b) shows the TG-DTA curves of the mixture of the pre-
sintered intermediate and molten salt KCl. The slight weight loss over
the temperature range of 350600 C was attributed to the
crystallization process of olivine LiFePO4, involving a possible
reaction of carbon with residue oxygen and sublimation [6,17]. A
spiculate endothermal peak was observed at 751 C, accompanied with
large weight loss at higher temperatures, representing the melting
process of KCl. Therefore, it is reasonable to set the sintering
temperature at 755 C.
Fig. 2 shows the X-ray diffraction patterns of the as-prepared
LiFePO4 at 755 C sintered for different times. All the patterns fit the
olivine structure (JCPDS No. 81-1173) well except for the relatively
low intensity ratio of (131/111) in the pattern of the sample sintered for
1 h. No diffraction peaks of KCl and other impurities are observed.
This result indicates that the olivine phase can rapidly be obtained at a
moderate temperature by the MS method. Since the molten phase
shows a much higher ion diffusion rate than the solid phase, it can
facilitate the reaction and accelerate the crystallization process [15].
Fig. 3(A)(C) shows the FE-SEM images of LiFePO4 synthesized
by the MS method sintered for different times. In Fig. 3(A), there are
many sub-micrometer grains aggregating to regular particles with
diameter of about 2 m, in which the grains are not closely packed and
show obvious interface. When sintering time prolongs to 3 h, well-
shaped spherical primary particles are observed, as shown in Fig. 3(B).
The spherical particles range in size from 2 m to 4 m, and no
aggregation interface is found. Some darker irregular substance which
adhered to the spherical particles is found, which is identified as in-situ
formed carbon stemming from pyrolysis of sucrose. An image of a
selected spherical LiFePO4 particle sintered for 6 h is shown in Fig. 3
(C). The particle becomes round and smoother, with a diameter up to
6 m. For comparison, a SEM micrograph of LiFePO4 particles
synthesized by a conventional solid-state method is shown in Fig. 3(D).
The sintering condition is the same as that of the sample presented in
Fig. 3(B). It can be seen clearly that each particle in Fig. 3(D) is a kind
of secondary particle composed of small size grains, and the shape of
1262 J.-F. Ni et al. / Materials Letters 61 (2007) 12601264

Fig. 3. FE-SEM images of LiFePO4 synthesized by the MS method sintered at 755 C for (A) 1 h, (B) 3 h, and (C) 6 h, and synthesized by the conventional solid-state method (D).

the particle is irregular and rough. In order to further evaluate the
property of the as-prepared LiFePO4, tap density measurement was
carried out. The tap density of LiFePO4 prepared by the MS method
sintered for 3 h is 1.55 g cm 3, which is much larger than that of
LiFePO4 prepared by solid-state method in the same sintering
condition (only 1.20 g cm3), and than the value in literature [6]. In
general, the existence of a large number of vacancies, due to the
agglomeration phenomenon in packing powder, reduces the packing
degree and tap density. Because of good fluidity and low surface area,
the spherical particle exhibits less vacancy in packing powder than
irregular particles and leads to high tap density. In addition, with the
increase in particle size, the vacancies in the powder can further
decrease, which leads to higher tap density [18]. The high tap density
will benefit the enhancement of volumetric energy density, and
advance the application in large energy supplies.
Based on the evolution of SEM images with sintering time, the
formation of spherical particle was proposed as follows. First, a large
number of nanometer or sub-micron LiFePO4 grains grow in the KCl
molten phase. Then the grains aggregate together and form a micron
particle with irregular shape. The micron particle evolves its morphology
by a so-called dissolutionprecipitation route [14], and its shape
gradually turns into spherical shape at the effect of interfacial tension of
molten salt. Finally, the spherical particles are obtained.
From the discussion above, we can learn that the obtained spherical
LiFePO4 product is much dependent on the effect of KCl molten salt.
This is due to the special characters of molten salt such as high ion
diffusion rate, strong dissolving capability and large interfacial tension
[15,19]. In the salt melt, the crystallization process of LiFePO4
undergoes a route of dissolutionprecipitation controlled growth, as
discussed in detail by Yang et al. [14]. The dissolutionprecipitation

Fig. 4. Cyclic voltammograms of LiFePO4 sintered at 755 C for 3 h by the Fig. 5. Cycle performance of LiFePO4 prepared by the MS method. Inset is their
molten salt method. Scanning rate: 0.1 mV s 1, voltage range: 2.84.0 V. initial charge and discharge curves.
 J.-F. Ni et al. / Materials Letters 61 (2007) 12601264
Fig. 6. Cyclability of LiFePO4 sintered for 3 h at different discharge rates.
process allows the particle to rebuild its shape and morphology. Under
the effect of large interfacial intensity of molten salt, the particle has a
strong tendency to become spherical in shape to lower the surface
energy [20]. Therefore, with the proceeding of the dissolution
precipitation process and sphericization process, the LiFePO4
particles gradually exhibit spherical characteristic. If the reaction
time extends, the particles will become larger and smoother. Without
the effect of molten salt, LiFePO4 also possibly proceeds to the
dissolutionprecipitation route, but it usually needs higher temper-
ature and longer time to form sphere-like morphology. For example, the
sphere-like LiFePO4 product prepared by Prosini et al. was achieved by
treating the raw materials at 800 C for 16 h [3].
Fig. 4 presents the cyclic voltammograms of the typical LiFePO4
sample synthesized by the molten salt method. The first scanning cycle
shows a broad anodic peak and a spiculate cathodic peak, which are
due to the phase-transition process between LiFePO4 and FePO4. In the
following cycle, both the anodic and cathodic peaks become spiculate
and well-shaped, indicating the good reversibility of the as-prepared
LiFePO4.
Galvanostatic tests were carried out in the potential range of 4.0
2.0 V at a current density of 15 mA g 1 (0.1 C, 1 C was arbitrarily taken
to be 150 mA g 1). Fig. 5 shows the cycle performance of the as-
prepared LiFePO4, and the inset is their first charge and discharge
curves. They all exhibit the same flat discharge plateau at about 3.4 V
vs. Li with tiny voltage polarization, indicating good electrochemical
characteristics [1]. It is clear that LiFePO4 sintered for 3 h exhibits the
best electrochemical performance, due to good crystallinity and
suitable size. It can deliver an initial capacity of 130.3 mAh g 1 and
a capacity of 137.2 mAh g 1 at the 40th cycle. Note that the capacity is
based on the LiFePO4/C composite, which contains 3 wt.% carbon as
expected. The inactive carbon decreases the ratio of the active material,
leading to reduced capacity. The initial capacity is only about 77% of
the theoretical value of LiFePO4, mainly due to the existence of
inactive/low active regions in LiFePO4 particles originating from poor
ion diffusion kinetics [21]. An appreciable capacity increase after a few
cycles has been observed, and similar results have also been reported in
the literature [22,23]. The improved capacity is possibly related to slow
penetration of electrolyte through the micropores in the LiFePO4
particles. During the agglomeration process, the carbon coating thin
layer has a chance to incorporate into the inner of LiFePO4 particles,
resulting in defects such as micropores and hollows, as shown in Fig. 3
1263
(B). In addition, the carbon coating layer may be partly cracked at the
stress stemming from the volume change during Li extraction and
reinsertion, which allow the further penetration of the electrolyte [23].
The capacities of LiFePO4 sintered for 1 h, and 6 h are relatively low,
only 109.3 mAh g 1 and 126.1 mAh g 1, respectively. The former is
due to the relatively low crystallinity, as displayed in the XRD pattern,
and the latter mostly suffers from large particle size.
Fig. 6 shows the rate performance of the as-prepared LiFePO4 sintered
for 3 h. At a moderate rate of 0.5 C, we can obtain a capacity of 129 mAh
g 1. At a high rate of 5 C, we can obtain a capacity of 92 mAh g 1. This
good rate capability is most possible due to the improved conductivity
connection of both the inter-particle and the intra-particle by in-situ
carbon.
As discussed above, increase of sintering time results in larger
particle, which improves the tap density of LiFePO4 material, but it also
leads to poor electrochemical performance. As a result, it is important
to explore the optimal synthesis procedure to find the equilibrium point
between the contradictories. Moreover, we had to prepare LiFePO4 at a
relatively high temperature because of the high melting point of KCl,
which might result in undesired side effects. So it is also important to
explore other molten salts with lower melting point. Such work is still
under investigation in our laboratory.
4. Conclusions
We introduced a KCl molten salt method to prepare LiFePO4
and obtained well-crystallized, spherical products. The KCl
molten phase not only accelerated the crystallization process, but
also facilitated the formation of the spherical particles. The
spherical product shows a higher tap density, which will benefit
the enhancement of volumetric energy density. The LiFePO4
sample prepared at 755 C for 3 h shows the best electrochemical
performance. At a current density of 15 mA g 1 (0.1 C), this
sample can deliver an initial capacity of 130.3 mAh g 1 and a
capacity of 137.2 mAh g 1 at the 40th cycle. At a high discharge
rate of 5 C, it still can deliver a capacity of 92 mAh g 1. The
molten salt synthesis provides an effective method to rapidly
prepare olivine LiFePO4 product with regular shape and
morphology, so it will possibly achieve a wide-range application
to the production of LiFePO4.
Acknowledgements
We thank Dr. Xiang Hao for the kind help. This work was
partly funded by the Strategic High-Technology Basic Research
Foundation of Beijing (No. Z0004106040221).
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