The lithium extraction/insertion mechanism in Li2FeSiO4

The lithium extraction and insertion mechanism in the cathode material Li2FeSiO4 has been monitored by in situ X-ray diffraction and Mossbauer spectroscopy during the first two cycles. The residual amounts of Li2FeSiO4 and LiFeSiO4 in the fully charged and discharged states are 5% and 10%, respectively, on the basis of both Mossbauer spectroscopy and powder XRD studies; this is also in good agreement with the results of electrochemical measurements. The observed lowering of the potential plateau from 3.10 to 2.80 V during the first cycle can be explained by a structural rearrangement in which some of the Li ions (in the 4b site) and Fe ions (in the 2a site) become interchanged.

[1]  R. J. Hill,et al.  Quantitative phase analysis from neutron powder diffraction data using the Rietveld method , 1987 .

[2]  E. Jette,et al.  An X-Ray Study of the Wstite (FeO) Solid Solutions , 1933 .

[3]  M. Armand,et al.  Surface chemistry of carbon-treated LiFePO4 particles for Li-ion battery cathodes studied by PES , 2003 .

[4]  Tsutomu Ohzuku,et al.  Electrochemistry of manganese dioxide in lithium nonaqueous cell. I: X-ray diffractional study on the reduction of electrolytic manganese dioxide , 1990 .

[5]  Robert Dominko,et al.  Structure and electrochemical performance of Li2MnSiO4 and Li2FeSiO4 as potential Li-battery cathode materials , 2006 .

[6]  Peter G. Bruce,et al.  Solid-state chemistry of lithium power sources† , 1997 .

[7]  Michel Armand,et al.  Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material , 2005 .

[8]  Dominique Guyomard,et al.  The Li1+xMn2O4/C rocking-chair system: a review , 1993 .

[9]  Juan Rodríguez-Carvajal,et al.  Recent advances in magnetic structure determination by neutron powder diffraction , 1993 .

[10]  N. N. Greenwood,et al.  Mössbauer studies of Fe1–xO. Part I. The defect structure of quenched samples , 1972 .

[11]  John B. Goodenough,et al.  Electrochemical extraction of lithium from LiMn2O4 , 1984 .

[12]  J. Dahn,et al.  Application of in situ Mossbauer effect methods for the study of electrochemical reactions in lithium-ion battery electrode materials , 1999 .

[13]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[14]  A. Jacobson,et al.  In situ Mössbauer spectroscopy studies of the electrochemical reaction of lithium with KFeS2 , 1979 .

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

[16]  C. Keffer,et al.  Crystal structure of twinned low-temperature lithium phosphate , 1967 .

[17]  Peter R. Slater,et al.  Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO4 Olivine-Type Battery Material , 2005 .

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

[19]  John T. Vaughey,et al.  Phase transitions in lithiated Cu2Sb anodes for lithium batteries: an in situ X-ray diffraction study , 2001 .

[20]  J. Dahn,et al.  In Situ Mössbauer Effect Studies of the Electrochemical Reaction of Lithium with Mechanically Alloyed Sn2Fe , 1998 .

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

[22]  Tsutomu Ohzuku,et al.  Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell , 1990 .