J.

of Advanced Engineering and Technology

Vol. 1, No. 1 (2008) pp. 107-111

Electrochemical Characteristics of LiFePO with Conductivity Materials 4

for Lithium Polymer Batteries

En Mei Kim, Kyung-Hee Park, and Hal-Bon Gu †

Department of Electrical Engineering, Chonnam National University,

300 Yongbong-dong, Buk-gu, Gwangju 500-757, South Korea
(Received : Aug. 14, 2008, Revised : Aug. 26, 2008, Accepted : Aug. 30, 2008)

Abstract : Phospho-olivine LiFePO cathode materials were prepared by hydrothermal reaction. In this study,
4

Multi-walled carbon nanotube (MWCNT) and Carbon black was added to enhance the electrical conductivity of
LiFePO . LiFePO , LiFePO -MWCNT and LiFePO -C particles were characterized by X-ray diffraction (XRD),
4 4 4 4

field emission scanning electron microscope (FE-SEM) transmission electron microscope (TEM). LiFePO /SPE/ 4

Li, LiFePO -MWCMT/SPE/Li and LiFePO -C/SPE/Li cells were characterized electrochemically by charge/
4 4

discharge experiments at a constant current density of 0.1 mA cm− in a range between 2.5 and 4.3 V vs. Li/Li
2 +

and cyclic voltammetry (CV). The results showed that initial discharge capacity of LiFePO was 103 mA h g− . 4
1

The discharge capacity of LiFePO -MWCNT/SPE/Li cell with 5 wt. % MWCNT was 124 mAh g− , LiFePO -C/
4
1
4

SPE/Li cell with 5 wt. % carbon black was 128 mAh g− at the first cycle. 1

Keywords : LiFePO , multi-walled carbon nanotube, carbon black, SPE

4

1. Introduction compatibility with environment[12,13]. However, it is difficult

to attain its full capacity because its electronic conductivity is
Since the commercialization of rechargeable lithium-ion batteries very low, and diffusion of Li ion in the olivine structure is
+

by Sony Energy Tech.[1] 17 years ago, they have been widely slow. It is found that small amount of Fe is oxidized to Fe2+ 3+

utilized as the power sources in a wide range of applications,
such as mobile phones, laptop computers, cameras, electrical
vehicles (EV), and hybrid electrical vehicles (HEV). In the
rechargeable lithium ion batteries, cathode material is the key
component, and mainly devoted to the performance of the batteries.
Among the known cathode materials, the layered LiCoO
LiMnO and LiNiO , spinel LiMn O , and elemental sulfur have
2 2 2 4
during hydrothermal process or annealing process[14,15]. There
are two methods to improve the electronic conductivity. One
method is to introduce conductive additives including carbon
coating[16-20] and supervalent cation doping[21,22]. Another
method is to control the particle size by optimizing the synthesis
2, conditions[23].
In this study, phosphor-olivine LiFePO was prepared by 4

been studied extensively[2-8]. LiCoO has been nowaday sutilized

2 hydrothermal reaction. In order to enhance the electrical conductivity
for commercial lithium-ion batteries. However, the above materials of LiFePO , conductivit materilas as carbon black and MWCBT
4

such as LiCoO possess high cost, environmental pollution and

2 was added. LiFePO /Li and LiFePO -C/Li cells were fabricated
4 4

thermal in stability and novel cathode material must be developed in anargon-filled glove box and their electrochemical properties
not only in relation to battery performance, but also inrelation were analyzed by means of CV and charge-discharge experiments.
to safety and cost.
Recently, lithium transition metal phosphates with an ordered 2. Experimental
olivine-type structure, LiMPO (M = Fe, Mn, Ni, and Co), have
4

attracted extensive attention due to a high theoretical specific LiFePO was prepared with starting materials of LiOH H O
4
.
2

capacity (170 mAh/g) [9-11]. The potential of the M /M redox 3+ 2+

(Aldrich Co. 99.95%), FeSO ·7H O (Ald-rich Co. 99 + %), H PO
4 2 3 4

couple versus Li/Li of LiMPO is as follows; 3.5 V for LiFePO ,

+
4 4 (Aldrich Co. 99.999 + %) and C H O (Aldrich Co. 99 + %).
6 8 6

4.1 V for LiMnPO , 5.2-5.4 V for LiNiPO , and 4.8 V discharge

4 4 After LiOH·H O was dissolved indistilled water to obtain 1
2

plateau for LiCoPO . Among these phosphates, LiFePO is

4 4 M solution, H PO and FeSO °§7H O powders were added to
3 4 4 2

the most attractive because of its high stability, low cost, high LiOH solution in a molar ratio for Li : Fe : P = 3 : 1 : 1. Addition
of ascorbic acid as a reducing agent to the precursor was
†
Corresponding Author useful in prohibiting the conversion of Fe to Fe during the2+ 3+

Tel : 062-530-1746
E-mail : hbgu@chonnam.ac.kr hydrothermal reaction and generation of α-Fe O during the 2 3

107
108 En Mei Jin, Kyung-Hee Park, Hal-Bon Gu

annealing process. The mixed solution was heated at 150 C. o

2(a)). It is shown from Figure 2(b) and Figure 2(c) that the average
After being cooled to room temperature, the solution was particle size of LiFePO -C (5 wt.%) and LiFePO -MWCNT
4 4

filtered to separate the precipitate powder, the powder was (5 wt.%)is around 300 nm and LiFePO -MWCNT (5 wt.%)
4

washed with ultrapure water. The obtained powder was dried particle is connected each other by amorphous MWCNT.
at 100 C for 1 h under vacuum. The dried powders were
o
As can be seen from Figure 3(a), an amorphous layer is
further dried at 400 C for 1 h in nitrogen atmosphere. In order
o
clearly observed for the hydrothermally synthesized LiFePO , as 4

to improve low electron conduction of LiFePO , carbon blackand

4 shown in Figure 3(b) and Figure 3(b). To confirm how carbon
MWCNT was added 5 wt.%. black is dispersed in LiFePO -C (5 wt.%) powder, it is obvious
4

The crystalline phases were identified with X-ray diffraction from the image that the surfaces of LiFePO powders are coated
4

(XRD, Dmax/1200, Rigaku). The X-ray diffraction pattern was by carbon coating layer and added MWCNT in LiFePO particles 4

collected by a step-scanning mode in the range of 10 ~80 o o

decreased between particles of traveling distance.
with a step time of 5 /min. Powder morphologies were observed
o
Cycling performance of LiFePO /Li, LiFePO -C (5 wt.%)/SPE/
4 4

by TEM (JEOL JEM-2000FXII) and Particle size distribution. Li and LiFePO -MWCNT (5wt.%)/SPE/Li cells are shown in Figure
4

A composite electrode was prepared by mixing LiFePO , 4 4, Figure 5 and Figure 6, respectively. As can be seen from Figure
LiFePO -C or LiFePO -MWCNT with 5 wt.% and polyvinylidene
4 4 4, the discharge capacity of LiFePO /SPE/Li cell is 103 mAh/g at
4

fluoride (PVdF) in a weight ratio of 70 : 25 : 5. The obtained
slurry was ball-milled for 1 h, and coated onto an Al-foil. The
resulting electrode films were pressed with a twin roller, cut
into a round plate (Φ = 15.958 mm) and dried at 110 C for 24
the first cycle and 86 mAh/g after 30 cycles, respectively.
In order to improved not good of cycling stability we added
to carbon balck and MWCNT. The cycling performand of
o
LiFePO -C (5 wt.%)/SPE/Li cell is shown in Figure 5. The initial
4

h under vacuum. Solid state electrolyte 25PVDFLiClO EC PC 4 10 10 discharge capacity of LiFePO -C (5 wt.%) is 128 mAh/g, and
4

as SPE was prepared by mixing of LiClO , propylene carbonate

4 after 30 cycles the discharge capacity is 126 mAh/g, respectively. It
and ethylene carbonate in a mole ratio of 1 : 10 : 10, and is demonstrated that cycling performance of LiFePO -C (5 wt.%)
4

finally polyvinylidenefluoride-hexafluoropropylene (Kynar2801) was /SPE/Li cell is better than that of LiFePO /SPE/Li cell and the
4

added. The coin-type (CR2032) cells were fabricated for the cycling stability is good than that of LiFePO /SPE/Li cell (Figure 4).
4

electrochemical tests. LiFePO /SPE/Li, LiFePO -C/SPE/Li and

4 4 Figure 6 shows cycling performance of LiFePO -MWCNT 4

LiFePO -MWCNT/SPE/Li coin-type cells were assembled with

4 (5wt.%)/SPE/Li cell. The initial discharge capacity of LiFePO - 4

lithium metal as anode and 25PVDFLiClO EC PC as SPE 4 10 10 MWCNT (5 wt.%) is 124 mAh/g, and after 30 cycles the discharge
in an argon-filled glove box. Charge/discharge testing was performed capacity is 126 mAh/g, respectively. It is demonstrated that cycling
using automatic charge/discharge equipment (WBCS 3000, performance of LiFePO -MWCNT (5 wt.%)/SPE/Li cell is better
4

WonaTech Co.) in a potential range of 2.5-4.3 V at aconstant and the cycling stability is good than that of LiFePO /SPE/Li 4

current density of 0.1 mA/cm . The CV testing was performed

2

using WBCS 3000 (WonATech Co.) battery tester system in a

potential range of 2.3-4.5 V at a scanning rate of 0.1 mVs− . 1

The test batteries were cycled galvanostatically in a potential

range of 2.5-4.3 V using a WBCS 3000 (WonATech Co.) battery
tester system at a constant current density of 0.1 mA cm− . 2

Electrochemical impedance measurements were performed using

an IM6 impedance system (Zahner Elektrik Company). The spectrum
was potentiostatically measured by applying an ac voltage of
10mV over the frequency range from 1 MHz to 10 mHz.

3. Results and discussion

XRD patterns of LiFePO , LiFePO -C and LiFeO -MWCNT
4 4 4

powders are shown in Figure 1. All the patterns can be indexed

to a single-phase material having an orthorhombic olivine-
type structure (space group Pmnb), which are the same as the
standard value (JCPD card number: 40-1499). No impurity is
found in all the LiFePO -C powders.
4

FE-SEM images of LiFePO LiFePO -MWCNT and LiFePO -

4, 4 4

C with 5 wt.% are shown in Figure 2. As can be seen from Figure 2, Figure 1. XRD patterns of LiFePO4 (a), LiFePO4-C (5 wt%) (b),
the average particle size of LiFePO is around 350 nm (Figure
4
LiFePO4-MWCNT (5 wt%) (c).

공학기술논문지 제1권 제1호 (2008)

 Electrochemical Characteristics of LiFePO4 with Conductivity Materials for Lithium Polymer Batteries 109

Figure 2. FE-SEM image of LiFePO4 (a), LiFePO4-C (5 wt%) (b),

LiFePO4-MWCNT (5 wt%) (c).

(Figure 4) and LiFePO -C/SPE/Licell (Figure 5).

4

Impedance spectra of LiFePO /SPE/Li, LiFePO -C/SPE/Li

4 4

and LiFePO - MWCNT/SPE/Li cells at constant current density

4

of 0.1 mAcm− upon cycling are shown in Figure 7. The batteries

2

were cycled between 2.5 and 4.3 V. It is noted that the ac

impedance response of the cell forms abroad semicircle and a Figure 3. TEM images of LiFePO4 (a), LiFePO4-C (5 wt%) (b),
line to the real axis in the lowest frequency range. The semicircle LiFePO4-MWCNT (5 wt%) (c).
in the high frequency is mainly related to the complex reaction
process at the electrolyte/cathode interface including resistance of to-particle contact resistance, charge transfer resistance, and
SEI film formed on the surface LiFePO particles, the particle-
4 corresponding capacitances. The inclined line in the lower frequency

J. of Adv. Eng. and Tech., Vol. 1, No. 1 (2008)

110 En Mei Jin, Kyung-Hee Park, Hal-Bon Gu

Figure 4. Cycling performance of LiFePO4/SPE/Li cell. Figure 5. Cycling performance of LiFePO4-C/SPE/Li cell.

is attributed to the Warburg impedance, which is associated

with lithium ion diffusion in LiFePO electrode. As can be 4

seen from Figure 7(a), the resistance is 150 Ω at the first

cycle, 220 Ω after 5 cycles, 300 Ω after 10 cycles, respectively.
It is obvious that LiFePO /SPE/Li cell resistance increases
4

upon the cycling. As can be seen from Figure 6(b), the resistance
is about 150 Ω at the first cycle, 5 and 10 cycles. It is obvious
that LiFePO -C/SPE/Li cell with 5 wt% carbon black resistance
4

hardly changes upon the cycling, and as can be seen from LiFePO - 4

MWCNT/SPE/Li cell (Figure 7(c)) with MWCNT 5wt.%, the

resistance is about 162 Ω at the first cycle, 163 Ω after 5
cycles, 159 Ω after 10 cycles, respectively. It is obvious that
LiFePO -C/SPE/Li and LiFePO -MWCNT/SPE/Li cell with 5wt%
4 4

resistance hardly change supon the cycling. It is noted that the

length of the inclined line in LiFePO /SPE/Li cell is longer thant
4

hat of the inclined line in LiFePO -C/SPE/Li and LiFePO -4 4

MWCNT/SPE/Li cell with 5 wt% conductivity materials, that is Figure 6. Cycling performance of LiFePO4-MWCNT/SPELi cell.
to say, lithium ion diffusion in LiFePO -C and LiFePO -MWCNT
4 4

electrode is faster than that in LiFePO electrode, therefore, as

4 The discharge capacity of LiFePO -C/SPE/Li cell with 5 wt.%
4

can be seen from Figure 5 and Figure 6, cycling performance of carbon black was 128 mAh/g at the first cycle and 126 mAh/g
LiFePO -C/SPE/Li and LiFePO -MWCNT/SPE/Li cell is better
4 4 after 30 cycles, respectively. The discharge capacity of LiFePO - 4

than that of LiFePO /SPE/Li cell.

4 MWCNT/SPE/Li cell with 5 wt.% MWCNT was 124 mAh/g
at the first cycle and 126 mAh/g after 30 cycles, respectively. It
4. Conclusion was demonstrated that cycling performance of LiFePO -C 4

(5 wt.%)/SPE/Li cells was better than that of LiFePO /SPE/Li

4

Phospho-olivine LiFePO cathode materials were prepared

4 cells and LiFePO -MWCNT (5 wt.%)/SPE/Li cell was better
4

by hydrothermal reaction. Carbon black and MWCNT as than that of another cells.
conductivity materials were added to enhance the electrical
conductivity of LiFePO Lithium polymer cells with LiFePO ,
4. 4 Acknowledgments
LiFePO -C (5 wt.%) and LiFePO -MWCNT (5 wt.%) as cathode
4 4

materials and 25PVDFLiClO EC PC as SPE were evaluated.

4 10 10 This research project received supporting funds from the
The discharge capacity of LiFePO /SPE/Li cell is 103 mAh/g
4 second-stage Brain Korea21.
at the first cycle and 86 mAh/g after 30 cycles, respectively.

공학기술논문지 제1권 제1호 (2008)

 Electrochemical Characteristics of LiFePO4 with Conductivity Materials for Lithium Polymer Batteries 111

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J. of Adv. Eng. and Tech., Vol. 1, No. 1 (2008)