Advanced Powder Technology 25 (2014) 16881692

Contents lists available at ScienceDirect

Advanced Powder Technology

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

Original Research Paper

Hydrothermal synthesis of spindle-shape and craggy-faced LiFePO4/C

composite materials for high power Li-ion battery
Weiyan Yu a,b, Lili Wu a,b,, Jinbo Zhao c, Yanpeng Zhang a,b, Gaozeng Li a,b
a

Key Laboratory for Liquid-Solid Structural Evolution and Process of Materials (Ministry of Education), Shandong University, Jinan 250061, China
School of Materials Science and Engineering, Shandong University, Jinan 250061, China
c
School of Materials Science and Engineering, Shandong Polytechnic University, Jinan 250353, China
b

a r t i c l e

i n f o

Article history:
Received 27 January 2014
Received in revised form 19 May 2014
Accepted 12 June 2014
Available online 25 June 2014
Keywords:
LiFePO4/C
Hydrothermal method
Pyrogallic acid
Spindle shape
Craggy-faced

a b s t r a c t
The large surface area and excellent conductivity are two important factors for LiFePO4 to achieve high
power capability in Li-ion batteries. This paper presents a hydrothermal method to obtain large surface,
spindle-shape and carbon-coated LiFePO4 particles. Pyrogallic acid was added to serve as reducing agent,
surface growth directing template and carbon source to synthesize craggy-faced LiFePO4/C composite
materials. It helps to control the morphology and implement carbon coating on the particles. The LiFePO4/
C particle synthesized with 8 wt.% pyrogallic acid demonstrates excellent electrochemical performance,
cyclic ability and rate capability.
2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
Among the Li-ion battery cathode materials, the olivine LiFePO4 has attracted great attention owing to its potential application as a cathode material. It possesses high theoretical capacity,
environmental benignity, particularly high thermal stability, outstanding high-rate capacity, excellent cycle performance and
cheap cost [16]. It is occupying the rapid demand in the market
for Electric Vehicles (EVs) and Plug-in Hybrid Electric Vehicles
(PHEVs) [2]. However, the poor electronic conductivity and slow
lithium ion diffusion block the lithium ion battery for high-end
consumers need [6,7]. Numerous attempts have been made to
improve its intrinsic drawback by carbon coating and ion doping
in crystal [812]. The LiFePO4 nanoparticles can be embedded in
a nanoporous carbon matrix [13] or be Carbon-Nanotube-Decorated [14] to get superior high-rate performance for lithium-ion
batteries.
It is also suggested that lithium ion diffusion kinetics is the
direct aspect related to superior high-power electrochemical
properties and the ability of lithium ion to travel across the interface between LiFePO4 and electrolyte phase is crucial for ultra-fast
Corresponding author at: Key Laboratory for Liquid-Solid Structural Evolution
and Process of Materials (Ministry of Education), Shandong University, Jinan
250061, China. Tel.: +86 531 88392724.
E-mail address: wulili02002@yahoo.cn (L. Wu).

diffusion [15]. Creating large surface area in electrode materials

could be conducive to the high-rate capability by shortening
the lithium ion diffusion path and increasing the interfacial
contact between active particles and the surrounding electrolyte
[1619].
Recently, a few synthetic methods have been used to prepare
large-surface LiFePO4. Zhao et al. [6] have synthesized LiFePO4 nanospheres in tridimensional porous carbon framework. This LiFePO4/C composite possesses the considerably enhanced electronic
conductivity of about 10 2 S cm 1 and amazing high surface area
of 200.5 m2 g 1, and the lithium ion diffusion gets up to 10 15
10 14 cm2 s 1. Sun et al. [20] demonstrated a novel solvothermal
synthesis of large scale LiFePO4 microspheres consisting of nanoparticles with an open three-dimensional porous microstructure.
These LiFePO4 microspheres show excellent rate capability and
cycle stability.
In this report, we rst demonstrate by adding pyrogallic acid to
synthesize craggy-faced and spindle-shape LiFePO4 via hydrothermal method. Due to the adsorption of the assistant agent molecules onto the particle surface during the particle growth [21], a
proper assistant agent in hydrothermal systems can tune the particle size and morphology. In this procedure, pyrogallic acid was
used as template agent, reducing agent as well as carbon source.
It is attractive in hydrothermal reaction as a synthetic medium.
Effects of the template agent on the morphology and microstructures of LiFePO4 are studied.

http://dx.doi.org/10.1016/j.apt.2014.06.012
0921-8831/ 2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

W. Yu et al. / Advanced Powder Technology 25 (2014) 16881692

1689

2. Experimental
2.1. Synthesis
The powder of LiFePO4 was synthesized using LiOH
H2O, FeSO4
7H2O, H3PO4 and pyrogallic acid. The starting precursor solution
was prepared in 3:1:1 molar ratio using the source materials. First,
Fe2+ salt (0.6 mol/L) and H3PO4 water solution were prepared and
mixed together. Pyrogallic acid was added to avoid the oxidation
of Fe2+ to Fe3+. Then LiOH
H2O was added to this solution and stirred the precursor for ve minutes. Ammonia was used to regulate
pH at 8.2. This mixture was then quickly transferred into a Teonlined stainless steel autoclave and heated at 180 C for 6 h. After
cooling to the room temperature, the precipitate was centrifuged
and washed with deionized water, then dried at 80 C for 6 h. Later,
these products were heat treated at 600 C for 4 h in Ar gas atmosphere to convert the residual pyrogallic acid to conductive carbon
coating to improve the conductivity and restrain the growth of the
products.
The samples obtained in this manner are hereafter abbreviated
as LFP1 (sample obtained with the ratio pyrogallic acid/LiFePO4 = 4:96 by wt. during synthesis), LFP2 (pyrogallic acid/LiFePO4 = 8:92 by wt.), LFP3 (pyrogallic acid/LiFePO4 = 16:84 by wt.).
2.2. Characterization
The crystallographic structure and purity of LiFePO4/C composite were examined by X-ray diffraction (XRD) with a Philips diffractometer using Cu Ka radiation. The diffraction data were collected
in the 2h-range between 15 and 80, with a step of 0.02. The
microstructure was observed using the eld emission scanning
electron microscope (FE-SEM, Hitachi S-4800) and the high-resolution transmission electron microscopy (HRTEM, JEM-2100) at
200 keV.
The electrochemical performances of LiFePO4 as cathode-active
materials were carried out by using a coin-type cell. The LiFePO4/C
composite was mixed and ground with carbon black and poly
vinylidene uoride uoride (PVDF) in the weight ratio of
75:15:10, dissolved in N-methylpyrrolidone (NMP) solvent to form
homogeneous slurry. The prepared slurry was spread on Al foil. The
coated electrodes were dried in vacuum at 120 C for 12 h to
remove NMP and moisture. The mass loading of these three electrodes were around 1.5 mg/cm2. The electrolyte consists of 1 M
LiPF6 in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1, volume). And the negative electrode was a lithium
metal foil. The cells were galvanostatically charged and discharged
between 2.5 V and 4.2 V versus Li/Li+ under different current densities at room temperature (25 C) on the electrochemical test
instrument (CT2001A, Wuhan Land Electronic Co. Ltd., China).
We include the carbon weight of composites to obtain the capacity
values.
3. Results and discussion
3.1. XRD analysis
Fig. 1 shows the XRD patterns of the samples synthesized with
the presence of pyrogallic acid. The results show that the wellresolved diffraction peaks of the three samples correspond to LiFePO4 indexed in space group Pnma [JCPDS Card No. 83-2092] and
the purity degree is high. No detectable reections corresponding
to carbon could be found in Fig. 1 due to its amorphous structure.
The diffraction peaks of the products are intensive and narrow. It
illustrates that the highly crystalline nature of LiFePO4 was
achieved.

Fig. 1. XRD patterns of (a) LFP1 (prepared with 4 wt.% pyrogallic acid), (b) LFP2
(prepared with 8 wt.% pyrogallic acid), and (c) LFP3 (prepared with 16 wt.%
pyrogallic acid).

3.2. Morphology studies

Morphologies of the LiFePO4 particles were examined by eld
emission scanning electron microscopy (FE-SEM). Fig. 2a and b
show the SEM images of LFP1 (prepared with 4wt.% pyrogallic
acid). The particles have a spindle shape with size distribution
ranging between 1 and 2 lm and a mid-diameter about 600 nm
(Fig. 2a). The particles have good dispersancy with little aggregation. This is mainly because that the hydroxyl of the pyrogallic acid
is easy to form hydrogen bond with the oxygen atoms. When the
nuclei formed, pyrogallic acid could easily adhere to the surface
of the nuclei at the O-terminate by the hydrogen-bonding interaction. During the crystal growth process, pyrogallic acid inuences
the ordering manner of the crystal growth, leading to the change
in crystal shape. It suggests that the pyrogallic plays the role of surface growth directing agent during the nucleation and growth
stage of the process. Furthermore, pyrogallic acid owns stereo-hindrance effect, which restrains the growth of the crystal nuclei and
prevents the aggregation of the particles [22]. In Fig. 2b, it can be
found that the particle surface is full of ravines. The rough face
could create a large surface area in active cathode materials,
enhancing the interfacial contact between active particles and
the surrounding electrolyte. It is conducive to the high-power
capability by reducing the transport resistance of electron and lithium ion during intercalation/de-intercalation process. Pyrogallic
acid plays a crucial role in controlling the morphology of LiFePO4.
While adding 8 wt.% pyrogallic acid (LFP2), the particle size and
shape does not change apparently as shown in Fig. 2c. But the surface of the particles becomes more rugged as seen in Fig. 2d. Fig. 2e
indicates that compared to the LFP2, the particle diameter
expanded after 16 wt.% pyrogallic acid added (LFP3). As seen in
Fig. 2f, the surface of the particles is etched with deep ridges. It
is rougher than LFP1 and LFP2.
The HRTEM image of LFP2 is presented in Fig. 3. From the
image, it could be seen that a uniform carbon coating layer is
formed on the surface of the LiFePO4 particles with a thickness
about 3.4 nm. Such carbon layer could raise the electronic conductivity of LiFePO4/C composite by connecting and wrapping the
LiFePO4 particles during the intercalation/de-intercalation process
[23]. Then, the pyrogallic acid plays three different roles: (i) it
serves as a reducing agent to avoid the oxidation of Fe2+ to Fe3+
under the hydrothermal condition. (ii) It controls the crystal

1690

W. Yu et al. / Advanced Powder Technology 25 (2014) 16881692

Fig. 2. FE-SEM images of (a and b) LFP1 (prepared with 4 wt.% pyrogallic acid), (c and d) LFP2 (prepared with 8 wt.% pyrogallic acid), and (e and f) LFP3 (prepared with 16 wt.%
pyrogallic acid).

3.3. Carbon coating structure

The disordering of the formed carbon was examined by Raman
spectroscopy in the range of 5003000 cm 1 (LabRam-1B with Ar
laser of 20 mW at 514 nm). The Raman spectra of LFP2 (prepared
with 8 wt.% pyrogallic acid) was shown in Fig. 4. Two peaks
were observed at 1595 and 1355 cm 1. The 1355 cm 1 band is
assigned to the D mode which is generally associated with the

Fig. 3. HRTEM image of LFP2 (prepared with 8 wt.% pyrogallic acid).

growth of LiFePO4. (iii) It provides a carbon source to carry on carbon coating during the post-heat process in Ar gas atmosphere.
Annealing can transform the pyrogallic acid into carbon coating
on the LiFePO4 particles surface to enhance the electronic conductivity and improve the crystallinity. The post-heat treatment did
not change the particle size signicantly, suggesting that the carbon coating inhibits the crystall growth during high temperature
heat treatment. The carbon content was measured by the weight
method. Weight analysis result shows the carbon content of
LFP1, LFP2 and LFP3 were respectively 2.2%, 5.4% and 7.5%.

Fig. 4. Raman spectra of LFP2 (prepared with 8 wt.% pyrogallic acid).

W. Yu et al. / Advanced Powder Technology 25 (2014) 16881692

1691

A1g symmetric vibration of amorphous carbon. The strong Raman

band at 1595 cm 1 is one of the E2g modes (or mode G), which
has been assigned to the vibrational mode of two neighboring carbon atoms in a graphene sheet. The peak intensity ratio ID/IG was
an index of the degree of disordering. The ID/IG of LFP2 was calculated to be 0.57, indicating that pyrogallic acid was pyrolyzed to
form graphitized carbons with a lower degree of disordering.
3.4. Electrochemical performances
Fig. 5 shows the initial chargedischarge proles of LFP1, LFP2
and LFP3 at 0.1 C. LFP1 exhibits a discharge capacity of
155.2 mA h/g with a small voltage difference between the charge
and discharge curves. The high discharge capacity could be partly
due to the larger particle surface area of the craggy-faced LiFePO4/
C composites which can contribute to the sufcient electrolyte
penetration to offer more active sites for electrochemical reactions
and shorten the diffusion path length of lithium ions [2426]. Furthermore, the established carbon coating layer is conducive to fast
electron transfer. The discharge capacity of LFP2 gets improved and
can get up to 163.9 mA h/g, which is close to the theoretical value
of 170 mA h/g. There is a smaller difference between the charge
and discharge curves than LFP1. The improvement could owe to
rougher particle surface which enhancing the ability of lithium
ions to travel across the interface between LiFePO4 and electrolyte
phase. However, with the quantity of pyrogallic acid increased to
16 wt.% (LFP3), the discharge capacity declines. LFP3 exhibit a discharge capacity of 139.7 mA h/g at 0.1 C only. This may attribute to
the signicant expansion of the particles diameter. Although pyrogallic acid could help to control the particle morphology and
increase the surface area, the extra addition augments the particle
size and lengthens the diffusion path of lithium ion, resulting in the
decline of the discharge capacity.
The rate capability of LFP2 was carried out. Fig. 6 displays the
rst charge and discharge curves of LFP2 at the current density
of 0.5 C, 1 C and 5 C. The LiFePO4/C sample exhibits specic capacities as high as 154.8 mA h/g at 0.5 C and 129.4 mA h/g at 1 C with
good power capability respectively. It also exhibits a high discharge capacity of 102.1 mA h/g and retains about 60% capacity
at 5 C. LFP2 shows a at discharge voltage at approximately
3.4 V, which is the typical electrochemical action of Li+ intercalation into FePO4. Craggy-faced particle synthesis can offer sufcient
electrolyte penetration and shorten the lithium ion diffusion path
of LiFePO4/C composite, enabling it to respond at high currents.

Fig. 6. The rst charge/discharge proles of LFP2 (prepared with 8 wt.% pyrogallic
acid) at different discharge rates ranging from 0.5 C to 5 C.

Fig. 7. Cyclic performance of LFP1, LFP2 and LFP3 measured at 0.1 C, 0.5 C and 1 C
charge and discharge rates (LFP1, prepared with 4 wt.% pyrogallic acid; LFP2,
prepared with 8 wt.% pyrogallic acid; LFP3, prepared with 16 wt.% pyrogallic acid).

Fig. 7 compares the rate capacity and cycle ability of LFP1, LFP2
and LFP3. LFP1 and LFP2 show a good cyclic ability and a better rate
capacity. Compared to LFP1 and LFP2, LFP3 shows lower rate
capacity with a signicant fade and poor cyclic ability at high currents. The capacity fade could be due to the diameter expansion
which increases the diffusion path length of the lithium ion and
therefore increases the charge transfer resistance, resulting in the
difculty of lithium ion insertion/ de-insertion during the charge/
discharge process.

4. Conclusion

Fig. 5. The initial charge/discharge curves of LFP1, LFP2 and LFP3 at 0.1C rate (LFP1,
prepared with 4 wt.% pyrogallic acid; LFP2, prepared with 8 wt.% pyrogallic acid;
LFP3, prepared with 16 wt.% pyrogallic acid).

In this article, spindle-shape and craggy-faced LiFePO4/C particles have been prepared through pyrogallic acid-mediated hydrothermal process. Pyrogallic acid played a crucial role in tailoring
the morphology of LiFePO4 nanostructure. It was used to serve as
reducing agent, surface growth directing template agent and carbon
source. The study demonstrates that larger particles surface areas
can allow better irrigation of the electrolyte and a shorter electronic
conduction path to enhance the capability of the lithium insertion/
de-insertion reaction. The obtained LiFePO4/C composite with
8 wt.% pyrogallic acid added exhibits excellent electrochemical

1692

W. Yu et al. / Advanced Powder Technology 25 (2014) 16881692

performance of 163.9 mA h/g at 0.1 C rate with good cycling performance and demonstrates high rate capability with about 60% capacity remained at 5 C rate. The pyrogallic acid assisted hydrothermal
method presents a facile and energy efcient way to produce high
performance olivine LiFePO4/C composite cathodes.
Acknowledgment
This work was nancially supported by the Foundation for
innovation funds of Shan-dong University, China (Program No.
2012TS030).
References
[1] A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, Phospho-olivines as
positive-electrode materials for rechargeable lithium batteries, J.
Electrochem. Soc. 144 (1997) 11881194.
[2] J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium
batteries, Nature 414 (2001) 359367.
[3] C. Delmas, M. Maccario, L. Croguennec, F.L. Cras, F. Weill, Lithium
deintercalation in LiFePO4 nanoparticles via a domino-cascade model, Nat.
Mater. 7 (2008) 665671.
[4] J. Barker, M.Y. Saidi, J.L. Swoyer, Batteries, fuel cells, and energy conversion
lithium iron(II) phospho-olivines prepared by a novel carbothermal reduction
method, Electrochem. Solid-State Lett. 6 (2003) A53A55.
[5] Y.Z. Li, Z. Zhou, M.M. Ren, X.P. Gao, J. Yan, Electrochemical performance of
nanocrystalline Li3V2(PO4)3/carbon composite material synthesized by a novel
solgel method, Electrochem. Acta 51 (2006) 64986502.
[6] J.Q. Zhao, J.P. He, J.H. Zhou, Y.X. Guo, T. Wang, S.C. Wu, X.C. Ding, R.M. Huang,
H.R. Xue, Facile synthesis for LiFePO4 nanospheres in tridimensional porous
carbon framework for lithium ion batteries, J. Phy. Chem. C 115 (2011) 2888
2894.
[7] A.S. Andersson, B. Kalska, L. Hggstrm, J.O. Thomas, A Lithium extraction/
insertion in LiFePO4: an X-ray diffraction and Mossbauer spectroscopy study,
Solid State Ionics 130 (2000) 4152.
[8] S. Chung, K. Bloking, Y. Chiang, Electronically conductive phospho-olivines as
lithium storage electrodes, Nat. Mater. 2 (2002) 123.
[9] G.X. Wang, S. Bewlay, J. Yao, J.H. Ahn, S.X. Dou, H. Liu, Batteries, fuel cells, and
energy conversion characterization of LiMxFe1 xPO4 (M = Mg, Zr, Ti) cathode
materials prepared by the solgel method, Electrochem. Solid-State Lett. 7
(2004) A503.
[10] K. Kim, J.H. Jeong, I.J. Kim, H.S. Kim, Carbon coatings with olive oil, soybean oil
and butter on nano-LiFePO4, J. Power Sources 167 (2007) 524528.

[11] N. Ravet, Y. Chouinard, J. Magnan, F.S. Besner, M. Gauthier, M. Armand,

Electroactivity of natural and synthetic triphylite, J. Power Sources 97 (98)
(2001) 503507.
[12] S. Xin, Y.G. Guo, L.J. Wan, Nanocarbon networks for advanced rechargeable
lithium batteries, Acc. Chem. Res. 45 (2012) 17591769.
[13] X.L. Wu, L.Y. Jiang, F.F. Cao, Y.G. Guo, L.J. Wan, LiFePO4 nanoparticles
embedded in a nanoporous carbon matrix: superior cathode material for
electrochemical energy-storage devices, Adv. Mater. 21 (2009) 27102714.
[14] X.L. Wu, Y.G. Guo, J. Su, J.W. Xiong, Y.L. Zhang, L.J. Wan, Carbon-nanotubedecorated nano-Lifepo4@C cathode material with superior high-rate and lowtemperature performances for lithium-ion batteries, Adv. Energy Mater. 3
(2013) 11551160.
[15] Y. Wang, Y. Yang, X. Hu, Y. Yang, H. Shao, Electrochemical performance of Rudoped LiFePO4/C cathode material for lithium-ion batteries, J. Alloys Comp.
481 (2009) 590594.
[16] B. Kang, G. Ceder, Battery materials for ultrafast charging and discharging,
Nature 458 (2009) 190193.
[17] R. Dominko, M. Bele, J.M. Goupil, M. Gaberscek, D. Hanzel, I. Arcon, J. Jamnik,
Wired porous cathode materials: a novel concept for synthesis of LiFePO4, J.
Chem. Mater. 19 (2007) 29602969.
[18] H. Yang, X.L. Wu, M.H. Cao, Y.G. Guo, Solvothermal synthesis of LiFePO4
hierarchically dumbbell-like microstructures by nanoplate self-assembly and
their application as a cathode material in lithium-ion batteries, J. Phys. Chem.
C 113 (2009) 33453351.
[19] J. Su, X.L. Wu, C.P. Yang, J.S. Lee, J. Kim, Y.G. Guo, Self-assembled LiFePO4/C
nano/microspheres by using phytic acid as phosphorus source, J. Phys. Chem. C
116 (2012) 50195024.
[20] J.F. Qian, M. Zhou, Y.L. Cao, X.P. Ai, H.X. Yang, Template-free hydrothermal
synthesis of nanoembossed mesoporous LiFePO4 microspheres for highperformance lithium-ion batteries, J. Phys. Chem. C 114 (2010) 34773482.
[21] C.W. Sun, S. Rajasekhara, J.B. Goodenough, F. Zhou, Monodisperse Porous
LiFePO4 Microspheres for a high power Li-ion battery cathode, J. Am. Chem.
Soc. 133 (2011) 21322135.
[22] D. Jugovic, M. Mitric, M. Kuzmanovic, N. Cvjeticanin, S. Markovic, S. kapin, D.
Uskokovic, Rapid crystallization of LiFePO4 particles by facile emulsionmediated solvothermal synthesis, Powder Techonol. 219 (2012) 128134.
[23] J.M. Tarascon, N. Recham, M. Armand, J.-N. Chotard, P. Barpanda, W. Walker, L.
Dupont, Hunting for better Li-based electrode materials via low temperature
inorganic synthesis, J. Chem. Mater. 22 (2010) 724739.
[24] C.H. Mi, X.G. Zhang, X.B. Zhao, H.L. Li, Synthesis and performance of
LiMn0.6Fe0.4PO4/ nano-carbon webs composite cathode, Mater. Sci. Eng., B
129 (2006) 813.
[25] H.M. Xie, R.S. Wang, J.R. Ying, L.Y. Zhang, A.F. Jalbout, H.Y. Yu, G.L. Yang, X.M.
Pan, Z.M. Su, Optimized LiFePO4polyacene cathode material for lithium-ion
batteries, Adv. Mater. 18 (2006) 26092613.
[26] J.F. Ni, H.H. Zhou, J.T. Chen, X.X. Zhang, Molten salt synthesis and
electrochemical properties of spherical LiFePO4 particles, Mater. Lett. 61
(2007) 12601264.