Electronically conductive phospho-olivines as lithium storage electrodes

Lithium transition metal phosphates have become of great interest as storage cathodes for rechargeable lithium batteries because of their high energy density, low raw materials cost, environmental friendliness and safety. Their key limitation has been extremely low electronic conductivity, until now believed to be intrinsic to this family of compounds. Here we show that controlled cation non-stoichiometry combined with solid-solution doping by metals supervalent to Li+ increases the electronic conductivity of LiFePO4 by a factor of ∼108. The resulting materials show near-theoretical energy density at low charge/discharge rates, and retain significant capacity with little polarization at rates as high as 6,000 mA g−1. In a conventional cell design, they may allow development of lithium batteries with the highest power density yet.

[1]  John O. Thomas,et al.  Lithium extraction/insertion in LiFePO4: an X-ray diffraction and Mossbauer spectroscopy study , 2000 .

[2]  Tatsuji Numata,et al.  Verwey-Type Transition and Magnetic Properties of the LiMn2O4Spinels , 1997 .

[3]  J. Papike,et al.  Crystal Chemistry of Silicate Minerals of Geophysical Interest , 1976 .

[4]  S. Kikkawa,et al.  Characterization of oxygen-deficient phases appearing in reduction of the perovskite-type LaNiO3 to La2Ni2O5 , 1995 .

[5]  Peter Y. Zavalij,et al.  Reactivity, stability and electrochemical behavior of lithium iron phosphates , 2002 .

[6]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[7]  Vladimir G. Tsirelson,et al.  Multipole analysis of the electron density in triphylite, LiFePO4, using X‐ray diffraction data , 1993 .

[8]  Hajime Arai,et al.  Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds , 1996 .

[9]  J. Rodríguez-Carvajal,et al.  Hole and Electron Doping of R2BaNiO5 (R = Rare Earths) , 1994 .

[10]  K. Amine,et al.  OLIVINE LICOPO4 AS 4.8 V ELECTRODE MATERIAL FOR LITHIUM BATTERIES , 1999 .

[11]  Hiroyuki Kageyama,et al.  5 V lithium cathodes based on spinel solid solutions Li2Co1+XMn3-XO8: -1 ≤ X ≤ 1 , 1999 .

[12]  A. Goñi,et al.  Magnetic properties of the LiMPO 4 (M = Co, Ni) compounds , 1996 .

[13]  John B. Goodenough,et al.  Effect of Structure on the Fe3 + / Fe2 + Redox Couple in Iron Phosphates , 1997 .

[14]  Per Kofstad,et al.  Nonstoichiometry, diffusion, and electrical conductivity in binary metal oxides. , 1972 .

[15]  Tadeusz Bak,et al.  Modification in the electronic structure of cobalt bronze LixCoO2 and the resulting electrochemical properties , 1989 .

[16]  E. C. Subbarao,et al.  Advances in Ceramics , 1981 .

[17]  P. Prosini,et al.  Improved electrochemical performance of a LiFePO4-based composite cathode , 2001 .

[18]  N. Nachtrieb,et al.  The chemistry of imperfect crystals , 1973 .

[19]  Sai-Cheong Chung,et al.  Optimized LiFePO4 for Lithium Battery Cathodes , 2001 .

[20]  T. L. Mercier,et al.  Li / β ‐ VOPO 4: A New 4 V System for Lithium Batteries , 1999 .

[21]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[22]  R. Schock,et al.  Electrical conduction in olivine , 1989 .

[23]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[24]  Linda F. Nazar,et al.  Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates , 2001 .

[25]  P. Wyder,et al.  Magnetoelectric properties of LiCoPO4: microscopic theory , 1999 .

[26]  John O. Thomas,et al.  Thermal stability of LiFePO4-based cathodes , 1999 .

[27]  N. L. Peterson Point Defects and Diffusion Mechanisms in the Monoxides of the Iron-Group Metals , 1984 .