Opportunities and challenges of Lithium Manganese

Iron Phosphates as positive electrode materials for 5

LiFePO4
Lithium Ion batteries 4.5 LiMn0.70Fe0.30PO4
LiMn0.80Fe0.20PO4
LiMn0.90Fe0.10PO4
4
N. Tran, G. Nuspl, C. Vogler and N. Schall LiMnPO4

U [V]
3.5

Süd Chemie AG, BEE-Battery, Ostenriederstr. 15, D- 3

85368 Moosburg 2.5

2
Corresponding author: Dr Nicolas Tran, 1.5
Nicolas.Tran@sud-chemie.com ; 0 20 40 60 80 100 120 140 160 180
Tel: +49 8761 82 283; Fax: +49 8761 82 339 Specific discharge capacity (mAh/g)

Figure 1: First specific discharge capacity of Süd Chemie’s C-

LiMn1-xFexPO4 electrodes (x = 0.0; 0.1; 0.2; 0.3; 1.0) measured
Much attention is paid to the carbon coated at 25°C in EC: DMC 1:1/ 1M LiPF6 electrolyte. The charging
LiFePO4 material for large format Lithium Ion batteries procedure was C/10 followed by a CV step until C/100.
because of the large availability of iron raw materials, the
excellent safety properties and the high charge/discharge 5
rate capability of the related lithium ion batteries (1-2). 4.5
However, there is a strong need for high energy density
4
for automotive applications.

U [V]
3.5

The carbon coated lithium manganese phosphate 3 C/10 CV C/100 - D/10

offers in principle similar safety behaviour but a larger 2.5 1C CV C/100 - 1D

energy density because of its larger voltage (4.1 V vs. Li) 2

1C CV C/100 - 3D

compared to the iron system (3.45 V vs. Li). The 1C CV C/100 - 5D

1.5
synthesis of electroactive C-LiMnPO4 proved to be 0 20 40 60 80 100 120 140 160 180
difficult (3-4). Downsizing this material and substitution
Specific discharge capacity (mAh/g)
of manganese by iron has been shown effective to
enhance the reversible capacity (3-6). Figure 2: Specific discharge capacity of a Süd Chemie’s C-
LiMn0.70Fe0.30PO4 electrode measured at various rates during
Samples of LiMn1-xFexPO4 (0 ≤ x ≤ 1) positive cycling at 25°C in EC: DMC 1:1/ 1M LiPF6. The batteries were
electrode materials were prepared by a precipitation charged in CCCV mode.
process (7). Their electrochemical properties were tested
in laboratory lithium cells and compared to those of Süd
5
Chemie’s LiFePO4. LiMn0,70Fe0,30PO4 D/10 - C/10 CV C/100
4.5 1D - 1C CV C/100
Pilot plant 1D- 1C CV C/10
A significant improvement of energy density 4 1D - 1C CV C/5
1D - 1C CV C/2.5
versus LiFePO4 has been proven for the C-
U [V]

3.5
LiMn0.70Fe0.30PO4 as shown in Figure 1. Moreover, a good
3
discharge rate capability could be demonstrated for C-
LiMn0.70Fe0.30PO4 electrodes (140 mAh/g at 5C) when the 2.5
batteries are slowly and completely charged as reported in 2
Figure 2.
1.5
0 20 40 60 80 100 120 140 160 180
Three main characteristics of the C-LiMn1-xFexPO4 Specific discharge capacity
batteries were observed during the electrochemical tests at [mAh/g]
RT:
(i) The battery charge conditions have a large impact on Figure 3: Influence of charging conditions on the discharge
the achieved discharge capacity and energy density, capacity for a Süd Chemie’s C-LiMn0.70Fe0.30PO4 electrode
especially when the manganese content in the measured at 25°C in EC: DMC 1:1/ 1M LiPF6. The lithium
olivine material approaches 100%, as shown in batteries were charged in CCCV mode until various current
Figure 3. limits.
(ii) A significant polarisation in the 4V region is
observed at discharges rates > 1C. (1) Padhi A.K., Nanjunsdaswamy K.S., Goodenough J.B., J.
Electrochem. Soc., 144, 1188-1194, 1997.
(iii) The length of the 4V pseudo plateau decreases upon
(2) Ravet N. et al, Meeting of the Electrochemical Society,
cycling or after a rate capability test, while the Honolulu, HI, Oct 17-22, 1999.
specific discharge capacity remains quasi constant. (3) J. Yao, S. Bewlay, K. Konstantinov, V.A. Drozd, R.S. Liu,
X.L. Wang, H.K. Liu and G.X. Wang, JAC, 425, 362-366, 2006.
The electrochemical characteristics of C-LiMn1-xFexPO4 (4) A. Yamada, M. Hosoya, S.C. Chung, Y. Kudo, K.
are compared to those of C-LiFePO4 and the reasons for Hinokuma, K.Y. Liu, Y. Nishi, JPS, 119-121, 223-238, 2003.
the lower activity of the 4V region for the manganese (5) Drezen T., Kwon N.H., Bowen P., Teerlinck I., Isono M. and
based materials will be discussed during the meeting. Exnar I., J. Power Sources, 949-953, 2007.
(6) S. K. Martha, B. Markovsky, J. Grinblat, Y. Gofer, O. Haik,
E. Zinigrad, D. Aurbach, T. Drezen, D. Wang, G. Deghenghi
and I. Exnar, JES, 156 (7), A541-A552, 2009.
(7) G. Nuspl, L. Wimmer and M. Eisgruber, WO2005/051840,
2005.