Interface investigations of a commercial lithium ion battery graphite anode material by sputter depth profile X-ray photoelectron spectroscopy.

Here we provide a detailed X-ray photoelectron spectroscopy (XPS) study of the electrode/electrolyte interface of a graphite anode from commercial NMC/graphite cells by intense sputter depth profiling using a polyatomic ion gun. The uniqueness of this method lies in the approach using 13-step sputter depth profiling (SDP) to obtain a detailed model of the film structure, which forms at the electrode/electrolyte interface often noted as the solid electrolyte interphase (SEI). In addition to the 13-step SDP, several reference experiments of the untreated anode before formation with and without electrolyte were carried out to support the interpretation. Within this work, it is shown that through charging effects during X-ray beam exposure chemical components cannot be determined by the binding energy (BE) values only, and in addition, that quantification by sputter rates is complicated for composite electrodes. A rough estimation of the SEI thickness was carried out by using the LiF and graphite signals as internal references.

[1]  L. Huang SOLID ELECTROLYTE INTER-PHASE ON GRAPHITE ANODES IN Li-ION BATTERIES , 2014 .

[2]  M. Winter,et al.  Investigation of lithium carbide contamination in battery grade lithium metal , 2012 .

[3]  M. Winter,et al.  SEI-forming mechanism of 1-Fluoropropane-2-one in lithium-ion batteries , 2012 .

[4]  L. Castro,et al.  Aging Mechanisms of LiFePO4 // Graphite Cells Studied by XPS: Redox Reaction and Electrode/Electrolyte Interfaces , 2012 .

[5]  Hung-Chun Wu,et al.  Effect of C60 ion sputtering on the compositional depth profiling in XPS for Li(Ni,Co,Mn)O2 electrodes , 2011 .

[6]  P. Novák,et al.  A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries , 2010 .

[7]  Xuejie Huang,et al.  Research on Advanced Materials for Li‐ion Batteries , 2009 .

[8]  A. Shard,et al.  XPS topofactors: determining overlayer thickness on particles and fibres , 2009 .

[9]  Dirk Uwe Sauer,et al.  Relevance of energy storage in future distribution networks with high penetration of renewable energy sources , 2009 .

[10]  P. Biensan,et al.  Surface film formation on electrodes in a LiCoO2/graphite cell: A step by step XPS study , 2007 .

[11]  J. Yamaki,et al.  TG-MS analysis of solid electrolyte interphase (SEI) on graphite negative-electrode in lithium-ion batteries , 2006 .

[12]  M. Mohai XPS MultiQuant: a step towards expert systems , 2006 .

[13]  Kristina Edström,et al.  A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries , 2006 .

[14]  Rémi Dedryvère,et al.  Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study , 2005 .

[15]  M. Wohlfahrt‐Mehrens,et al.  Ageing mechanisms in lithium-ion batteries , 2005 .

[16]  M. Wagner,et al.  XRD evidence for the electrochemical formation of Li+(PC)yCn- in PC-based electrolytes , 2005 .

[17]  M. Broussely,et al.  Main aging mechanisms in Li ion batteries , 2005 .

[18]  Sylvie Grugeon,et al.  XPS Identification of the Organic and Inorganic Components of the Electrode/Electrolyte Interface Formed on a Metallic Cathode , 2005 .

[19]  D. R. Penn,et al.  Calculations of electron inelastic mean free paths , 2005 .

[20]  Kristina Edström,et al.  The cathode-electrolyte interface in the Li-ion battery , 2004 .

[21]  Kristina Edström,et al.  Characterisation of the SEI formed on natural graphite in PC-based electrolytes , 2004 .

[22]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.

[23]  R. Kostecki,et al.  Characterization of SEI Layers on LiMn2O4 Cathodes with In Situ Spectroscopic Ellipsometry , 2004 .

[24]  M. Wagner,et al.  Electrolyte Decomposition Reactions on Tin- and Graphite-Based Anodes are Different , 2004 .

[25]  Margret Wohlfahrt-Mehrens,et al.  Aging mechanisms of lithium cathode materials , 2004 .

[26]  Guy Sarre,et al.  Aging of lithium-ion batteries , 2004 .

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

[28]  Martin Winter,et al.  Acrylic acid nitrile, a film-forming electrolyte component for lithium-ion batteries, which belongs to the family of additives containing vinyl groups , 2003 .

[29]  K. Möller,et al.  A study on electrolyte interactions with graphite anodes exhibiting structures with various amounts of rhombohedral phase , 2003 .

[30]  K. Edström,et al.  Electrochemically lithiated graphite characterised by photoelectron spectroscopy , 2003 .

[31]  D. R. Penn,et al.  Calculation of electron inelastic mean free paths (IMFPs) VII. Reliability of the TPP‐2M IMFP predictive equation , 2003 .

[32]  James W. Evans,et al.  Characterization of the SEI on a Carbon Film Electrode by Combined EQCM and Spectroscopic Ellipsometry , 2003 .

[33]  Richard T. Haasch,et al.  Surface Characterization of Electrodes from High Power Lithium-Ion Batteries , 2002 .

[34]  Andrea G. Bishop,et al.  The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes , 2002 .

[35]  Martin Winter,et al.  Advances in battery technology: rechargeable magnesium batteries and novel negative-electrode materials for lithium ion batteries. , 2002, Chemphyschem : a European journal of chemical physics and physical chemistry.

[36]  Kristina Edström,et al.  Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite , 2001 .

[37]  Martin Winter,et al.  Fluorinated organic solvents in electrolytes for lithium ion cells , 2001 .

[38]  P. Novák,et al.  FTIR and DEMS investigations on the electroreduction of chloroethylene carbonate-based electrolyte solutions for lithium-ion cells , 1999 .

[39]  E. Peled,et al.  A Study of Highly Oriented Pyrolytic Graphite as a Model for the Graphite Anode in Li‐Ion Batteries , 1999 .

[40]  P. Ross,et al.  The Reaction of Lithium with Dimethyl Carbonate and Diethyl Carbonate in Ultrahigh Vacuum Studied by X-ray Photoemission Spectroscopy , 1999 .

[41]  Ralph E. White,et al.  Capacity Fade Mechanisms and Side Reactions in Lithium‐Ion Batteries , 1998 .

[42]  Petr Novák,et al.  Chloroethylene carbonate, a solvent for lithium ion cells, evolving CO2 during reduction , 1998 .

[43]  Martin Winter,et al.  Insertion reactions in advanced electrochemical energy storage , 1998 .

[44]  Doron Aurbach,et al.  A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate‐Dimethyl Carbonate Mixtures , 1996 .

[45]  D. Aurbach,et al.  X-ray photoelectron spectroscopy studies of lithium surfaces prepared in several important electrolyte solutions. A comparison with previous studies by Fourier transform infrared spectroscopy , 1996 .

[46]  H. Tamura,et al.  Morphology and chemical compositions of surface films of lithium deposited on a Ni substrate in nonaqueous electrolytes , 1995 .

[47]  D. Aurbach,et al.  The application of EQCM to the study of the electrochemical behavior of propylene carbonate solutions , 1995 .

[48]  Martin Winter,et al.  Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes , 1995 .

[49]  D. Aurbach,et al.  Impedance spectroscopy of lithium electrodes , 1994 .

[50]  H. Tamura,et al.  XPS analysis of a lithium surface immersed in propylene carbonate solution containing various salts , 1992 .

[51]  Doron Aurbach,et al.  Identification of Surface Films Formed on Lithium in Propylene Carbonate Solutions , 1987 .

[52]  B. Scrosati,et al.  A Cyclable Lithium Organic Electrolyte Cell Based on Two Intercalation Electrodes , 1980 .

[53]  Emanuel Peled,et al.  The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model , 1979 .