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Abstract
Olivine structured LiFePO4/carbon composites with different amounts of carbon were prepared by a modied two-step solid-state reaction.
The iron citrate used as both iron and carbon sources in the reaction resulted in the formation of carbon coatings on the olivine particles as the
mixed precursors were heated at three different initial-step temperatures of 200, 300 and 400 1C followed by a second-step annealing at moderate
temperatures of 700 1C. The obtained nal powders with varying carbon contents were systematically analyzed by characterization techniques of
thermo-gravimetric analysis, X-ray powder diffraction, eld-emission scanning electron microscopy, and eld-emission transmission electron
microscopy prior to electrochemical testing in order to determine the structural and calcination effects on the electrochemical properties of the
composites. The eld-emission transmission electron microscopy images revealed that the morphology of the LiFePO4 composites consist of
agglomerated particles surrounded by carbon as a conductive material. Among the prepared samples, the LiFePO4/carbon composite calcined at
initial-step temperature of 300 1C showed the highest discharge capacity and the best rate capability in the voltage range of 2.54.2 V.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Lithium iron phosphate; Cathode materials; Solid-state synthesis; Lithium-ion batteries
1. Introduction
Rechargeable Li-ion batteries are considered as an attractive
power source for a variety of applications including cellular
phones, notebook computers, camcorders and even electric
vehicles. Although LiCoO2 is currently the most widely
applied cathode material in commercial lithium-ion batteries
owing to its decent electrochemical properties and convenience
of preparation, it is not free from disadvantages of low
practical capacity, high cost, toxicity and inferior safety
features [1,2]. In recent years, NASICON or olivine-type
materials built from MO6 octahedron (where M is Fe, Co,
Mn, Ni, V or Ti) and strongly covalent bonded tetrahedral
polyanions (XOn4 , where X is P, W, S or Mo), have been
investigated as cathodes with signicant structural stability
[36]. Among these, LiFePO4 remains a promising candidate
n
Corresponding author. Tel.: +82 62 530 1703; fax: +82 62 530 1699.
E-mail address: jaekook@chonnam.ac.kr (J. Kim).
0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.07.043
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2. Experimental
TGA
DTA
100
1.0
90
Weight (%)
80
0.5
70
60
0.0
50
40
-0.5
30
0
200
400
600
800
110
1000
Temperature (C)
106
106
104
104
102
102
Weight (%)
100
100
1.07%
98
98
96
94
pure LFP
92
LFP/C-400
90
90
12.4%
LFP/C-200
86
0
200
400
94
92
LFP/C-300
88
96
6.05%
600
800
88
86
1000
Temperature (C)
Fig. 1. (a) TG/DTA curves for precursor (the mixture of Li2CO3, FeC6
H5O7 xH2O and NH4H2PO4) after ball-milling in air atmosphere, (b) TG
curves for the LFP/C-200, LFP/C-300 and LFP/C-400 composites formed by
initial pre-heating at 200, 300 and 400 1C, respectively in air atmosphere and
subsequent calcination at 700 1C in Argon atmosphere compared with that of
pure LiFePO4.
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Table 1
Lattice parameters, unit cell volume values, and carbon contents from elemental analysis of LFP/C-200, LFP/C-300 and LFP/C-400 composites.
Sample name
a ()
b ()
c ()
LFP/C-200
LFP/C-300
LFP/C-400
10.3333
10.3300
10.3280
6.0103
6.0073
6.0129
4.6912
4.6895
4.6919
291.3546
291.0087
291.3770
9.206
3.176
0.838
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Fig. 2. XRD patterns of (a) LFP/C-200, (b) LFP/C-300 and (c) LFP/C-400
composites prepared by a two-step solid state reaction.
Fig. 3. FE-SEM images of (a) LFP/C-200, (b) LFP/C-300 and (c) LFP/C-400 composites with different carbon contents and corresponding HR-TEM images
showing the carbon covered particles in the (d) LFP/C-200, (e) LFP/C-300 and (f) LFP/C-400 composites and indicating the formation of the carbon layer.
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4.5
200
0.7C
1.4C
2.8C
5.5C
11C
160
3.5
3.0
LFP/C-400
LFP/C-300
LFP/C-200
2.5
0
20
40
60
0.17C 0.35C
4.0
120
80
LFP/C-400
LFP/C-300
LFP/C-200
40
12
15
18
21
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4. Conclusions
LiFePO4/C composites with different amount of carbon contents
were successfully synthesized by a modied two step solid-state
reaction without adding any extra carbon source during synthesis.
During the preparation of the composites, the initial-step temperatures were chosen between 200 and 400 1C whereas the second
step annealing was performed at a common moderated temperature
of 700 1C. The present study investigated the effects of pre-heating
temperature on the electrochemical behavior of the LFP/C
composites. The results showed that controlling the pre-heating
temperature inuences the generation of in-situ carbon layer
thickness and hence improving the performance of the LiFePO4/
C cathodes. It is also observed that the thickness and content of the
carbon coating can be controlled by choosing the appropriate preheat calcination temperature. Increasing the pre-heating temperature
leads to a decrease in the carbon content. The amounts of carbon
were investigated by elemental analysis and found to be 9.206 wt
%, 3.176 wt% and 0.838 wt% for the LiFePO4/carbon composites
calcined at 700 1C after pre-heating at 200 1C, 300 1C and 400 1C
respectively. The carbon in the LiFePO4/C composites is obtained
from the citrate anion which is used as a precursor and a carbon
source during the solid-state reaction process. The carbon can
suppress the growth of the LiFePO4 particles during the annealing
process and enhance the electronic conductivity of the composites.
The XRD results showed that the materials had an olivine structure
(space group: Pnma) and complete crystallization without any
impurities. The TEM images also conrmed the carbon coating on
the surface of the LiFePO4 particles. Among the prepared
composites, the sample pre-heated at 300 1C showed better
electrochemical performance. When employed as a cathode in a
lithium test cell, LFP/C-300 cathode delivered an initial discharge
capacity of 160 mA h g 1 at a current density of 28.9 mA
g 1(0.17 C). Even at a high current density of 11 C, this
composite still presents a discharge capacity of 101 mA h g 1 in
the voltage range of 2.54.2 V versus Li/Li+ at room temperature.
These improved electrochemical performances can be attributed to
the uniform carbon coating of 7 nm thickness which may facilitate
an enhancement in electronic conduction and also promote lithium
ion diffusion. This comparative study reveals the necessity of
forming a conductive coating along with particle size reduction
for improving the electrochemical properties of LiFePO4 at high
C-rates.
Acknowledgments
This work was supported by Priority Research Centers Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education, Science and Technology (20090094055).
References
[1] B. Scrosati, Challenge of portable power, Nature 373 (1995) 557558.
[2] A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, Phospho-olivines
as positive-electrode materials for rechargeable lithium batteries, Journal
of the Electrochemical Society 144 (1997) 11881194.
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