Improved Cyclic Performance of Lithium-Ion Batteries: An Investigation of Cathode/Electrolyte Interface via In Situ Total-Reflection Fluorescence X-ray Absorption Spectroscopy

For the further development of lithium-ion batteries, improvement of their cyclic performance is crucial. However, the mechanism underlying the deterioration of the battery cyclic performance is not fully understood. We investigated the effects of the electronic structure at the electrode/electrolyte interface on the cyclic performance of the cathode materials via in situ total-reflection fluorescence X-ray absorption spectroscopy. In a LiCoO2 thin-film electrode that exhibits gradual deterioration upon subsequent Li ion extractions and insertions (cycling), the reduction of Co ions at the electrode/electrolyte interface was observed upon immersion in an organic electrolyte, with subsequent irreversible changes after cycling. In contrast, in a LiFePO4 thin-film electrode, the electronic structure at the electrode/electrolyte interface was stable and reversible upon electrolyte immersion with subsequent cycling. The increased stability of the electronic structure at the LiFePO4/electrolyte interface affect...

[1]  R. Holze,et al.  Surface modifications of electrode materials for lithium ion batteries , 2006 .

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

[4]  Y. Koyama,et al.  Co K-edge XANES of LiCoO2 and CoO2 with a variety of structures by supercell density functional calculations with a core hole , 2012 .

[5]  Kazuo Yamamoto,et al.  Dynamic visualization of the electric potential in an all-solid-state rechargeable lithium battery. , 2010, Angewandte Chemie.

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

[7]  Minoru Inaba,et al.  Electrochemical AFM study of LiMn2O4 thin film electrodes exposed to elevated temperatures , 2008 .

[8]  C. Brouder,et al.  Angular dependence of core hole screening in LiCoO2 : A DFT+U calculation of the oxygen and cobalt K-edge x-ray absorption spectra , 2009, 0912.2894.

[9]  B. Jung,et al.  Effects of metal oxide coatings on the thermal stability and electrical performance of LiCoCO2 in a Li-ion cell , 2004 .

[10]  Y. Orikasa,et al.  Effects of ZrO2 Coating on LiCoO2 Thin-Film Electrode Studied by In Situ X-ray Absorption Spectroscopy , 2013 .

[11]  Rita Baddour-Hadjean,et al.  Raman microspectrometry applied to the study of electrode materials for lithium batteries. , 2010, Chemical reviews.

[12]  B. Cho,et al.  Effect of Al2O3 coating on electrochemical performance of LiCoO2 as cathode materials for secondary lithium batteries , 2004 .

[13]  C. Delmas,et al.  Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO2 to CoO2 Investigated by XPS , 2008 .

[14]  A. Wokaun,et al.  Synchrotron X-Ray Absorption Study of LiFePO4 Electrodes , 2005 .

[15]  Y. Koyama,et al.  Defect Chemistry in Layered LiMO2 (M = Co, Ni, Mn, and Li1/3Mn2/3) by First-Principles Calculations , 2012 .

[16]  Chaoyang Wang,et al.  Cycling degradation of an automotive LiFePO4 lithium-ion battery , 2011 .

[17]  Yoji Sakurai,et al.  Reaction behavior of LiFePO4 as a cathode material for rechargeable lithium batteries , 2002 .

[18]  Zhouguang Lu,et al.  Pulse Laser Deposition and Electrochemical Characterization of LiFePO4-C Composite Thin Films , 2008 .

[19]  Rongshun Wang,et al.  Long-term cyclability of LiFePO4/carbon composite cathode material for lithium-ion battery applications , 2009 .

[20]  Minoru Inaba,et al.  Preparation of c-axis oriented thin films of LiCoO2 by pulsed laser deposition and their electrochemical properties , 2001 .

[21]  I. Nakai,et al.  Study of the Jahn–Teller Distortion in LiNiO2, a Cathode Material in a Rechargeable Lithium Battery, byin SituX-Ray Absorption Fine Structure Analysis☆ , 1998 .

[22]  K. Amine,et al.  High-temperature storage and cycling of C-LiFePO4/graphite Li-ion cells , 2005 .

[23]  W. Yoon,et al.  Structural and Electrochemical Properties of LiAl y Co1 − y O 2 Cathode for Li Rechargeable Batteries , 2000 .

[24]  Sai-Cheong Chung,et al.  Crystal Chemistry of the Olivine-Type Li ( Mn y Fe1 − y ) PO 4 and ( Mn y Fe1 − y ) PO 4 as Possible 4 V Cathode Materials for Lithium Batteries , 2001 .

[25]  Kazuhisa Tamura,et al.  Surface Structure of LiNi0.8Co0.2O2: a New Experimental Technique Using in Situ X-ray Diffraction and Two-Dimensional Epitaxial Film Electrodes , 2009 .

[26]  Yong Yang,et al.  Recent advances in the research of polyanion-type cathode materials for Li-ion batteries , 2011 .

[27]  G. Ceder,et al.  The electronic structure and band gap of LiFePO4 and LiMnPO4 , 2004, cond-mat/0506125.

[28]  Hajime Arai,et al.  First in situ observation of the LiCoO2 electrode/electrolyte interface by total-reflection X-ray absorption spectroscopy. , 2012, Angewandte Chemie.