Electrochemistry Communications 7 (2005) 669–673

www.elsevier.com/locate/elecom

High-temperature storage and cycling of C-LiFePO4/graphite

Li-ion cells
K. Amine *, J. Liu, I. Belharouak
Electrochemical Technology Program, Chemical Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL 60439, USA

Received 12 April 2005; accepted 18 April 2005

Available online 23 May 2005

Abstract

The high-temperature storage and cycling characteristics of prismatic Li-ion cells with carbon-coated LiFePO4 cathodes, MCMB
graphite anodes and a LiPF6/EC–DEC electrolyte were investigated. The cells showed a significant capacity fade when cycled at 37
and 55 °C. Li–Sn reference electrode studies indicated that the interfacial impedance of the graphite electrode increased significantly
during high-temperature cycling. Carbon-coated LiFePO4 electrodes were found to release iron ions into the electrolyte when aged
at these temperatures; EDAX analyses confirmed the presence of iron at the surface of the graphite electrodes. The observed imped-
ance rise of the graphite electrodes and the consequent capacity fade of the cells were attributed to the formation of interfacial films
that were produced on the graphite electrodes as a result of possible catalytic effects of the metallic iron particles. The cycling sta-
bility of the cells was improved significantly when the LiPF6 electrolyte salt was replaced with the lithium bis-oxalatoborate
LiB(C2O4)2 salt.
Ó 2005 Elsevier B.V. All rights reserved.

Keywords: Li-ion battery; Olivine; LiFePO4; Lithium bis-oxalatoborate; High-temperature

1. Introduction metallic lithium counter electrodes. Few studies have

Recently, LiFePO4 with an olivine-type structure has
attracted significant interest as a cathode material for
Li-ion batteries because, it is proposed to be a low cost
material with excellent safety characteristics and also it
has the potential of providing a long cycle and calendar
life [1–8]. However, LiFePO4 is an insulating material,
which seriously limits its rate capability [2–4]. Recently,
extensive works have been conducted to enhance the
electronic conductivity of LiFePO4 by coating it with
carbon using either a carbon composite technique, such
as a carbon gel or sugar process [4–8] or by doping it
with <1% Nb5+ [7]. To date, most of the efforts to im-
prove the rate capability of LiFePO4 have focused on
carbon-coated electrodes (C-LiFePO4) in cells with
*
Corresponding author. Tel.: +1 630 252 3838; fax: +1 630 252 4176.
E-mail address: amine@cmt.anl.gov (K. Amine).
been made on the stability of LiFePO4 relative to the
electrolyte in a Li-ion cell configuration. In this paper,
we report results of high-temperature cycling studies of
LiFePO4/graphite and C-LiFePO4/graphite Li-ion cells
and the relative stability of LiFePO4 in electrolytes with
LiPF6 and lithium bis-oxalatoborate salts.
2. Experimental
LiFePO4 was prepared by solid-state reaction of a
1:1:1 (molar ratio) mixture of iron(II) oxalate, ammo-
nium di-hydrogen phosphate, and lithium carbonate.
The precursors were mixed by ball milling in acetone
overnight. The resulting gel was dried at 60 °C under
vacuum, thoroughly reground, and heated under puri-
fied N2 gas for 24 h at 700 °C. The resulting gray powder
was coated with carbon layers using a preheated flow of

1388-2481/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2005.04.018
670 K. Amine et al. / Electrochemistry Communications 7 (2005) 669–673

N2/C3H6 in a gas-phase process. This technique consists
of feeding a pre-heated reactor furnace containing LiFe-
PO4 with a mixture of N2 as inert gas and propylene
C3H6 as the carbon source gas [9]. The temperature at
which the cracking of C3H6 was achieved was fixed at
700 °C. The carbon content in the olivine was deter-
mined by thermogravimetry and was around 3.5 wt%.
X-ray diffraction confirms that LiFePO4 and C-LiFePO4
were pure phases. The electrochemical studies were car-
ried out on both LiFePO4 and C-LiFePO4 materials.
The LiFePO4 positive electrode consisted of 75 wt%
LiFePO4 active material, 15 wt% carbon black and
10 wt% polyvinylidinedifluoride (PVDF) coated onto
an aluminum foil current collector. In contrast, the C-
LiFePO4 electrode was made by coating a paste consist-
ing of 92 wt% C-LiFePO4 and 8 wt% PVDF (no carbon
black was added) onto an aluminum foil. The negative
electrode was made of 90 wt% MCMB graphite and
10 wt% PVDF binder coated onto a copper foil. The po-
sitive and negative electrodes were balanced to prevent
any lithium plating at the negative electrode during cy-
cling. The electrolytes were 1.2 M LiPF6 dissolved in a
(1:1:3 wt%) blend of ethylene carbonate (EC), propylene
carbonate (PC), and dimethyl carbonate (DMC); 1.2 M
angular range of 10–60° (2h) with a 0.02° (2h) step.
The unit cell parameters were calculated using a Riet-
veld profile matching refinement of the XRD diagrams
[10].
3. Results and discussion
Fig. 1 shows the XRD patterns of LiFePO4 olivine
before and after the coating experiment. The XRD pat-
tern of the non-coated olivine can be indexed according
to the space group Pnma of the orthorhombic system
with the parameters: a = 5.983, b = 10.289, and
c = 4.670 Å. No noticeable changes of the olivine
XRD pattern were observed for the carbon-coated
LiFePO4, which means that the olivine-type structure
was well maintained under our carbon coating experi-
mental conditions, with no evidence of impurities such
as Fe2P phosphide reported by others [7,14].
Fig. 2 shows the cycling performance of the C-LiFe-
PO4 electrode vs. the lithium counter electrode both at
25 and 55 °C. At room temperature C-LiFePO4

111

020

311
LiPF6 dissolved in EC and ethyl methyl carbonate After Coating
(EMC) (3:7 wt%); and 0.7 M LiB(C2O4)2 lithium bis-
101

401
121

610
222
200

oxalatoborate (LiBOB) dissolved in (EC:PC:DMC)

301

102
210

331
430
212
410

022
131
(1:1:3 wt%). High-temperature (37 and 55 °C) electro-

412
202
321
011

chemical tests were carried out on laser-sealed

110 mAh prismatic cells. The charge/discharge cycling
was carried out between 2.7 and 3.8 V at C/3 rate. The 10 20 30 40 50 60
micro-reference electrode was made of a 25-m copper
wire, insulated by a 3 lm layer of polyurethane enamel. Before Coating
The role of the insulation layer is to prevent any mixed
potential along the wire during the study. The insulation
layer was stripped from the tip of the wire using a strip-
ping solution, and a tin layer (1-lm thick) was electro-
plated onto the exposed copper. This micro-reference
electrode was placed between two separator membranes 10 20 30 40 50 60
to insulate it from both electrodes. After cell assembly, 2θ
the tin-plated layer on the tip of the wire was slightly Fig. 1. XRD patterns of LiFePO4 before and after coating with
charged with lithium from the positive electrode using carbon.
negligible quantities of active lithium (about 3.3 lAh)
to form, in situ, the Sn–Li alloy reference electrode.
Energy dispersive X-ray spectroscopy (EDXS) was 180
18
16
160
carried out using Hitachi S-4700-II FESEM equipment.
Capacity, mAh/g

14
140
AC impedance data were collected by a Schlumberger 12
120
model 1255 frequency response analyzer connected to 10
100 55˚˚C
55 C
a Schlumberger model 1286 electrochemical interface 80 RT
and a EG&G PAR 273 potentiostat. A small (20 mV) 60
AC perturbation plus a DC bias voltage equal to the cell 40
20
open-circuit-voltage (OCV) was applied with a fre- 0
quency sweep from 0.01 Hz to 100 kHz during the mea- 0 20 40 60 80 100
surements. Powder X-ray diffraction (XRD) patterns of Cycle Number
the olivine samples were recorded on a Siemens D5000 Fig. 2. Discharge capacity vs. cycle number of C-LiFePO4/Li cell at 25
powder diffractometer using CuKa radiation in the and 55 °C.
 K. Amine et al. / Electrochemistry Communications 7 (2005) 669–673
generates a capacity of 140 mAh/g at a C/3 rate with an
excellent cycle performance up to 100 cycles. At 55 °C,
the C-LiFePO4/Li cell shows a slightly higher capacity
of 158 mAh/g, mainly because at this temperature, the
electrolyte conductivity increases and the electrode wet-
ting characteristics are improved. The cell also cycles
well with a limited capacity fade after 100 cycles. These
cycling results are very comparable to those reported for
cells made of a carbon-coated LiFePO4 cathode using
different techniques [4–8].
Fig. 3 shows the cycling data of cells made of a non-
coated LiFePO4 as the positive electrode and MCMB
graphite as the negative electrode in the presence of a
1.2 M LiPF6/EC:DEC (3:7) electrolyte. At 37 °C, the cell
showed a significant capacity fade while no sign of
capacity decrease was observed up to 50 cycles at room
temperature. This result is very significant and tends to
contradict the reported stability of the olivine as the best
low cost and stable cathode material for the Li-ion bat-
teries [1–8]. Because of the poor cycling characteristic of
LiFePO4 at even 37 °C, it is very unlikely that, this sys-
tem will find a quick application as a cathode material
for the Li-ion batteries until this problem is addressed.
Similar high-temperature cycling results were also ob-
tained with a cell having carbon-coated olivine (C-LiFe-
PO4) as cathode and MCMB as anode (Fig. 4). In this
case, the prismatic cells with an average capacity of
110 mAh, were cycled between 2.7 and 3.8 V at room
temperature, 37 and 55 °C using LiPF6/EC:DEC (3:7)
as electrolyte at the C/3 rate. At room temperature,
the cell cycles extremely well with no capacity fade up
to 100 cycles. However, when increasing the temperature
to 37 and 55 °C, the cells show significant capacity loss
after 100 cycles especially at 55 °C. Similar capacity fade
was also reported when storing the cells at 3.8 V for four
weeks at 55 °C. These results show that the olivine sys-
1.2
1.0
Normalized capacity, (C/C1)
0.8
0.6
0.4
0.2
0.0
0 10 20 30
Cycle Number
Fig. 3. Normalized discharge capacity with cycled number at C/3 rate
of LiFePO4/MCMCB at 25 and 37 °C in the presence of 1.2 M LiPF6/
EC:EMC (3:7).
671
1.2
Normalized Capacity, C/C1
RT
1
0.8
37˚C
0.6
0.4 55˚C
0.2
0
0 20 40 60 80 100 120
Cycle Number
Fig. 4. Normalized discharge capacity with cycled number at C/3 rate
of C-LiFePO4/MCMB at 25, 37 and 55 °C. The electrolyte used is
1.2 M LiPF6/EC:EMC (3:7).
tem (coated or non-coated with carbon) has a major is-
sue with high-temperature cycling that is similar to that
reported in the manganese spinel system [11]. Unlike the
spinel system, the LiFePO4 olivine performs even worse
at 37 °C with significant capacity loss (Figs. 3 and 4). To
understand the reason behind the significant capacity
fade at 55 °C of the olivine system, the stability of LiFe-
PO4 and C-LiFePO4 in the presence of electrolyte was
investigated. An appropriate amount of either LiFePO4
or C-LiFePO4 powder was immersed in a 1.2 M LiPF6
in EC:DEC (3:7) electrolyte; the powder/electrolyte
solution was kept at 55 °C for one week. The solution
was then filtered and analyzed by the inductively cou-
pled plasma (ICP) technique to quantify traces of iron
ions that may have dissolved in the electrolyte. At the
end of this aging process, over 640 and 535 ppm of
Fe2+ ions were detected in the LiFePO4 and C-LiFePO4
electrolyte solution, respectively. These amounts are sig-
nificantly higher that the 90 ppm Mn2+ ions dissolution
reported in the case of the stabilized manganese spinel
(Li1.06Mn1.94O4) after four weeks of aging at 55 °C
[11]. This result indicates that Fe2+ ions may be present
in electrolytes during cycling or storage of LiFePO4-cells
25˚C at high-temperature. However, the amount of Fe2+ was
not so significant to account for the major capacity loss
observed for the cells cycled at 37 and 55 °C.
To investigate the origin of the significant capacity
37˚C
fade of the C-LiFePO4/graphite cells during cycling at
37 and 55 °C, the AC impedance of cells during cycling
at 55 °C was measured using a specially designed Li–Sn
reference electrode. The results are shown in Figs. 5 and
6. The AC impedance was measured after one formation
cycle at room temperature (Fig. 5) and after 50 cycles at
55 °C (Fig. 6). At the initial stages of cycling, the imped-
ances of the negative electrode and positive electrode
40 50 were very similar. However, after 50 cycles at 55 °C,
the impedance of the negative electrode increased signif-
icantly and accounted for almost 90% of the total cell
impedance. After achieving 50 cycles at 55 °C, the cell
was dissembled and the graphite anode was recovered
672 K. Amine et al. / Electrochemistry Communications 7 (2005) 669–673

3.0

2.5

2.0
-Z", Oh m

1.5
Cathode
Cell
1.0 Anode

0.5

0.0 Fig. 7. EDAX analysis of MCMB graphite negative electrode surface

0.0 0.5 1.1 1.5 2.0 2.5 3.0 after cell cycling at 55 °C; the presence of metallic iron on its surface is
Z' , Ohm observed.

Fig. 5. AC impedance of C-LiFePO4/graphite cell after 1 cycle at 25

°C using Li–Sn alloy reference electrode showing the impedance of the which theoretically should avoid the reduction of dis-
cell, the positive electrode and the negative electrode. The electrolyte
solved Fe-ions at the surface of this electrode. Fig. 8
used is 1.2 M LiPF6/EC:EMC (3:7).
shows the cycling performance of the C-LiFePO4/Li4-
Ti5O12 cell at 55 °C. The cell exhibits excellent capacity
35 retention (86% after 100 cycles) compared with the
C-LiFePO4/graphite cell. This result can be attributed
30 to the fact that the Fe2+ remains in the electrolyte and
is not reduced to metallic iron at the graphite surface.
25 A similar phenomenon was observed in the case of the
spinel manganese oxide [11]. In the case of the carbon-
coated olivine (C-LiFePO4), it has been reported that
-Z", Oh m

20
Anode the carbon coating process could result in the reduction
15 Cathode
of iron and the formation of Fe2P phosphide or
Cell
Fe75P15C10 phosphocarbides phases [14], which may dis-
10 solve in the electrolyte causing the capacity fade accord-
ing to the mechanism indicated above. However, this
5 hypothesis may not be true since significant iron dissolu-
tion and capacity fade was also observed for a pure
0 LiFePO4 with no carbon coating. In addition, No signs
0 5 10 15 20 25 30 35 of these phases were observed by an X-ray diffraction
Z' , Ohm analysis of both LiFePO4 and C-LiFePO4, for which
Fig. 6. AC impedance of C-LiFePO4/graphite cell after 50 cycles at
55 °C using Li–Sn alloy reference electrode indicates a significant
55 ˚C
impedance increase of the negative electrode after cycling. The
1.2
electrolyte used is 1.2 M LiPF6/EC:EMC (3:7).
Normalized Capacity, C/C1

1.0

and examined by the EDXS technique. The EDXS spec- 0.8

trum (Fig. 7) clearly showed the presence of Fe metal at
0.6
the graphite surface. It is thought that the dissolved Fe2+
was reduced at the graphite surface, whose potential is 0.4
ca. 0.06–0.1 V vs. Li°, and that the iron metal played a
catalytic role in the formation and growth of an interfa- 0.2
cial film at the graphite surface, leading to the huge rise 0.0
of the interfacial impedance of the negative electrode. 0 20 40 60 80 100
To prove this hypothesis, a cycling experiment was per- Cycle Number
formed using a Li4Ti5O12 spinel anode. In this case, Li4- Fig. 8. Cycling performance of C-LiFePO4/Li4Ti5O12 cell at 55 °C
Ti5O12 has a high nominal voltage, ca. 1.5 V vs. Li°, using 1.2 M LiPF6, EC/PC/DMC (1:1:3) electrolyte.
 K. Amine et al. / Electrochemistry Communications 7 (2005) 669–673 673

1.2
535 ppm
600 LiBOB
1.0

Normolized Capacity,C/C1
LiPF6
Fe content, ppm

500
0.8
400
300 0.6
<3.7 ppm
200
0.4
100

0 0.2
LiBOB LiPF6

Fig. 9. Amount of Fe2+ ions dissolved from C-LiFePO4 powder that
has been aged in 1.2 M LiPF6/EC:PC:DMC (1:1:3) and 0.7 M LiBOB/
EC:PC:DMC (1:1:3) for one week at 55 °C.
not only the XRD patterns were similar but also the par-
ticles sizes and morphology were near identical. To im-
prove the cycling performance of the olivine/graphite
system, it is very important to suppress the dissolution
of Fe from the olivine. One way to accomplish this is
to use an electrolyte salt that does not generate HF acid,
which could be in our case responsible for leaching the
iron ions from the surface of the olivine material. One
salt that has attracted significant attention because it
does not generate a strong acid is the LiBOB salt [11–
13]. In this case, LiBOB does not generate a strong
acidic environment when dissolved in an electrolyte
and therefore the rate of Fe2+ dissolution should be re-
duced. Fig. 9 shows the amount of Fe ions dissolved
from C-LiFePO4 powder after one week of aging the
material at 55 °C in 1.2 M LiPF6/EC:PC:DMC (1:1:3)
and 0.7 M LiBOB/EC:PC:DMC (1:1:3) electrolytes.
While more than 535 ppm of Fe ions were dissolved in
LiPF6-based electrolyte after only one week, less than
3.5 ppm was observed in the case of LiBOB-based elec-
trolyte. Fig. 10 shows the capacity fade of the C-LiFe-
PO4/graphite at 55 °C in the LiBOB and LiPF6-based
electrolytes. The capacity retention of the C-LiFePO4/
graphite Li-ion cell, with the LiBOB-based electrolyte,
was significantly better than for similar cells that used
the LiPF6-based electrolyte. Even though we observed
a significant improvement in capacity retention with
the use of the LiBOB-based electrolyte, the cell capacity
fade was still observed, but at a significantly reduced
rate. This is because the Fe2+ ions are still dissolving,
migrating to the negative electrode, and being reduced
at the electrode surface to cause an impedance increase
(similar to what occurs in LiPF6-based electrolytes,
but at a reduced rate).
0.0
0 20 40 60 80 100
Cycle Number
Fig. 10. Normalized discharge capacity with cycled number at C/3 rate
of C-LiFePO4/MCMB at 55 °C in 1.2 M LiPF6/EC:PC:DMC (1:1:3)
and 0.7 M LiBOB/EC:PC:DMC (1:1:3) electrolytes.
Acknowledgments
The authors acknowledge the financial support of the
US Department of Energy, FreedomCAR & Vehicle
Technologies Office, under Contract No. W-31-109-
Eng-38. Quallion LLC is also acknowledged for making
the prismatic cell for this study.
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