Massachusetts Institute of Technology Cambridge, 02139: and Solid State Letters 7 (2), A30 (2004)

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Improvement of the high rate performance of

LiFePO4
Byoungwoo Kang and Gerbrand Ceder
Department of materials science and engineering
Massachusetts Institute of Technology
Cambridge, Massachusetts, 02139

LiFePO4 is an interesting positive electrode


material for rechargeable lithium batteries because
the material is thermally and structurally stable. The
poor electronic conductivity which was believed to
be the obstacle for real applications has been solved
by several techniques such as carbon coating,
metallic layer coating and doping. We have further
tried to improve the high rate performance of the
material by adding a fast Li-ion conducting phase to
the system. We believe that this is particularly
important for LiFePO4 as theoretical results indicate
that it is a pure 1D Li conductor1. Hence rapid Li
transport to the surface facets that gives access to the Figure 2 Ragone plot for LiFePO4 and surface treated
diffusion channels may be important. The aim of this LiFePO4. The rate capability of surface treated
presentation is to demonstrate very high rate LiFePO4 shows better performance, especially at high
capability in LiFePO4 by using optimizing both ionic rates.
and electronic conductivities. 1
Morgan, D., Van der Ven, A., and Ceder, G.,
The most common way to improve transport Li conductivity in LixMPO4 (M = Mn, Fe,
characteristics is to minimize the of particle size. This Co, Ni) olivine materials. Electrochemical
strategy shortens the diffusion length of lithium and and Solid State Letters 7 (2), A30 (2004).
2
electron and works very well in LiFePO4 even Delacourt, C., Poizot, P., Levasseur, S., and
without carbon coating2,3. When transport in the Masquelier, C., Size effects on carbon-free
particle is fast enough, transport to the particle LiFePO4 powders. Electrochemical and
surface or insertion at the surface may become rate Solid State Letters 9 (7), A352 (2006).
3
limiting4. In this work we address this problem by Kim, D. H. and Kim, J., Synthesis of
coating the material with a Li-ion conducting phase. LiFePO4 nanoparticles in polyol medium
and their electrochemical properties.
LiFePO4 was synthesized by solid state Electrochemical and Solid State Letters 9
(9), A439 (2006).
reaction from Li2CO3, FeC2O4 ·2H2O, and NH4H2PO4. 4
Wang, L., Zhou, F., Meng, Y. S., and Ceder,
To prevent the iron from an oxidation, heat treatment
G., First-principles study of surface
was performed under inert environment. The lithium
properties of LiFePO4: Surface energy,
metal as anode and 1M-LiPF6 in EC/DMC (1:1) as
structure, Wulff shape, and surface redox
electrolyte were used for the electrochemical test
potential. Physical Review B 76 (16) (2007).
using the Swagelok type cell at room temperature. By
modifying the solid state reaction, we are able to
create small particles and ionically conducting
surface phases in a single processing step

Figure 1 SEM image of surface treated LiFePO4


materials. The particle size is around 50 nm.

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