In Situ Electrochemical XAFS Studies on an Iron Fluoride High-Capacity Cathode Material for Rechargeable Lithium Batteries

The reactions and structural evolution of FeF3 during cell cycling are investigated in an in situ cell by using Fe K-edge X-ray absorption fine-structure (XAFS) spectroscopy. The results of X-ray absorption near-edge structure spectroscopic analysis demonstrate that there are three stages in the reaction of FeF3 with Li: (1) a two-phase intercalation reaction in the range of x = 0 to 0.46 Li, (2) a single-phase intercalation reaction in the range of x = 0.46 to 0.92 Li, and (3) a conversion reaction in the range of x = 0.92 to 2.78 Li. The coordination numbers (CNs) and bond lengths of the Fe–F bonds or Fe–Fe bonds for the lithiated FeF3 are obtained by performing XAFS fitting. The splitting trends of the Fe–F bond lengths and the Fe–F CNs in the range of x = 0 to 0.92 Li support the proposal that R-3c-structured FeF3 is transformed into R3c-structured Li0.92FeF3 after the intercalation of 0.92 equiv. of Li, and that the intermediate Li0.46FeF3 may be R3-structured. The small Fe–Fe CN of Li2.78FeF3 indica...

[1]  Xingyan Wang,et al.  Synthesis and electrochemical performance of spherical FeF3/ACMB composite as cathode material for lithium-ion batteries , 2012, Journal of Materials Science.

[2]  Xiao‐Qing Yang,et al.  Investigation of the charge compensation mechanism on the electrochemically Li-ion deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 electrode system by combination of soft and hard X-ray absorption spectroscopy. , 2005, Journal of the American Chemical Society.

[3]  Ko Kang Ning,et al.  SYNTHESIS AND CHARACTERIZATION OF , 2011 .

[4]  Y. Ukyo,et al.  In situ XAFS and micro-XAFS studies on LiNi0.8Co0.15Al0.05O2 cathode material for lithium-ion batteries , 2006 .

[5]  K. Hodgson,et al.  A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes , 1997 .

[6]  Nathalie Pereira,et al.  Carbon-Metal Fluoride Nanocomposites Structure and Electrochemistry of FeF3: C , 2003 .

[7]  J. Rehr,et al.  Theoretical approaches to x-ray absorption fine structure , 2000 .

[8]  Lisa C. Klein,et al.  Investigation of the Lithiation and Delithiation Conversion Mechanisms of Bismuth Fluoride Nanocomposites , 2006 .

[9]  J. Tarascon,et al.  Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries , 2000, Nature.

[10]  J. Bearden.  X-Ray Wavelengths , 1967 .

[11]  M. Armand,et al.  Building better batteries , 2008, Nature.

[12]  C. Delmas,et al.  Non-cooperative Jahn-Teller effect in LiNiO2: An EXAFS study , 1995 .

[13]  S. Emura,et al.  Structural Change of Li1−xNi0.5Mn0.5O2 Cathode Materials for Lithium-ion Batteries by Synchrotron Radiation , 2003 .

[14]  G. Amatucci,et al.  In situ X-ray absorption spectroscopic investigation of the electrochemical conversion reactions of CuF2–MoO3 nanocomposite , 2010 .

[15]  Glenn G. Amatucci,et al.  Carbon Metal Fluoride Nanocomposites High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries , 2003 .

[16]  P. Balaya,et al.  Li-Storage via Heterogeneous Reaction in Selected Binary Metal Fluorides and Oxides , 2004 .

[17]  T. Ressler.  WinXAS: a program for X-ray absorption spectroscopy data analysis under MS-Windows. , 1998, Journal of synchrotron radiation.

[18]  D. Koningsberger,et al.  X-ray absorption : principles, applications, techniques of EXAFS, SEXAFS and XANES , 1988 .

[19]  Boon K. Teo,et al.  EXAFS: Basic Principles and Data Analysis , 1986 .

[20]  Baris Key,et al.  Identifying the local structures formed during lithiation of the conversion material, iron fluoride, in a Li ion battery: a solid-state NMR, X-ray diffraction, and pair distribution function analysis study. , 2009, Journal of the American Chemical Society.

[21]  J. Xu,et al.  Structural Studies of Lithium Intercalation in a Nanocrystalline α-Fe2O3 Compound , 2006 .

[22]  A. Barrière,et al.  Optical absorption study of iron trifluoride thin films , 1978 .

[23]  Hajime Arai,et al.  Cathode performance and voltage estimation of metal trihalides , 1997 .

[24]  A. Ankudinov,et al.  REAL-SPACE MULTIPLE-SCATTERING CALCULATION AND INTERPRETATION OF X-RAY-ABSORPTION NEAR-EDGE STRUCTURE , 1998 .

[25]  A. Beale,et al.  EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles. , 2010, Physical chemistry chemical physics : PCCP.

[26]  I. Nakai,et al.  X-ray absorption fine structure and neutron diffraction analyses of de-intercalation behavior in the LiCoO2 and LiNiO2 systems , 1997 .

[27]  I. Nakai,et al.  In situTransmission X-Ray Absorption Fine Structure Analysis of the Charge–Discharge Process in LiMn2O4, a Rechargeable Lithium Battery Material , 1997 .

[28]  M. Berrettoni,et al.  Characterization of Sol-Gel-synthesized LiFePO4 by multiple scattering XAFS. , 2006, Inorganic chemistry.

[29]  Meilin Liu,et al.  Nanostructured electrodes for lithium-ion and lithium-air batteries: the latest developments, challenges, and perspectives , 2011 .

[30]  Wei Zhang,et al.  Synthesis and characterization of in situ Fe2O3-coated FeF3 cathode materials for rechargeable lithium batteries , 2012 .

[31]  M. Newville,et al.  Estimation of measurement uncertainties in XAFS data , 1999 .

[32]  G. Amatucci,et al.  Bismuth Fluoride Nanocomposite as a Positive Electrode Material for Rechargeable Lithium Batteries , 2005 .

[33]  P. Novák,et al.  A multi-sample automatic system for in situ electrochemical X-ray diffraction synchrotron measurements. , 2007, Journal of synchrotron radiation.

[34]  H. Liebhafsky.  X-Ray Absorption , 1949 .

[35]  L. Gu,et al.  Low‐Temperature Ionic‐Liquid‐Based Synthesis of Nanostructured Iron‐Based Fluoride Cathodes for Lithium Batteries , 2010, Advanced materials.

[36]  Glenn G. Amatucci,et al.  Fluoride based electrode materials for advanced energy storage devices , 2007 .

[37]  G. Amatucci,et al.  Iron Oxyfluorides as High Capacity Cathode Materials for Lithium Batteries , 2009 .

[38]  L. Gu,et al.  A Mesoporous Iron‐Based Fluoride Cathode of Tunnel Structure for Rechargeable Lithium Batteries , 2011 .

[39]  Glenn G. Amatucci,et al.  Structure and Electrochemistry of Copper Fluoride Nanocomposites Utilizing Mixed Conducting Matrices , 2007 .