Phenomenologically modeling the formation and evolution of the solid electrolyte interface on the graphite electrode for lithium-ion batteries

Abstract The formation and evolution of the solid electrolyte interface (SEI) film during the first electrochemical intercalation of lithium into graphite were modeled as a special precipitation process including a nucleation phase of the SEI film's solid deposition, and followed by a growth phase involving the precipitation of new solids on previously formed solid nuclei. It was shown that the solid species can nucleate in the electrolyte solution, directly on the graphite surface, or adjacent to an already present particle on the graphite surface when precipitating from the electrolyte solution. Within the framework of classical nucleation theory (CNT), we can qualitatively explain the origin of the two-layer structure of SEI films, which consists of a thin, compact polycrystalline or heteromicrophase layer rich in inorganic species ( e.g. , LiF, Li 2 O) close to the electrode, and a thicker porous and amorphous layer composed mainly of organic compounds ( e.g. , ROLi, ROCO 2 Li) that is farther from the graphite.

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

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

[3]  Shinichiro Nakamura,et al.  Decomposition of LiPF6and Stability of PF 5 in Li-Ion Battery Electrolytes Density Functional Theory and Molecular Dynamics Studies , 2003 .

[4]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[5]  Doron Aurbach,et al.  On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries , 1999 .

[6]  Koichi Tanaka,et al.  Initial Reaction in the Reduction Decomposition of Electrolyte Solutions for Lithium Batteries , 2000 .

[7]  M. Broussely,et al.  Aging mechanism in Li ion cells and calendar life predictions , 2001 .

[8]  T. Gustafsson,et al.  Surface chemistry of intermetallic AlSb-anodes for Li-ion batteries , 2007 .

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

[10]  Doron Aurbach,et al.  The Application of Atomic Force Microscopy for the Study of Li Deposition Processes , 1996 .

[11]  L. Murr,et al.  Nucleation and growth characteristics of palladium and indium thin films , 1972 .

[12]  P. Balbuena,et al.  Lithium-ion batteries : solid-electrolyte interphase , 2004 .

[13]  Lei Gao,et al.  Characterization of Irreversible Processes at the Li/Poly[bis(2,3‐di‐(2‐methoxyethoxy)propoxy)phosphazene] Interface on Charge Cycling , 1997 .

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

[15]  P. Balbuena,et al.  Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: reduction mechanisms of ethylene carbonate. , 2001, Journal of the American Chemical Society.

[16]  D. Aurbach,et al.  Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems , 1997 .

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

[18]  M. Ishikawa,et al.  Effects of the Organic Solvent on the Electrochemical Lithium Intercalation Behavior of Graphite Electrode , 1996 .

[19]  P. Novák,et al.  The importance of the active surface area of graphite materials in the first lithium intercalation , 2007 .

[20]  D. Aurbach.  Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries , 2000 .

[21]  R. Kostecki,et al.  Electrochemical and Infrared Studies of the Reduction of Organic Carbonates , 2001 .

[22]  Jeff Dahn,et al.  Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells , 1990 .

[23]  A. Dey,et al.  The Electrochemical Decomposition of Propylene Carbonate on Graphite , 1970 .

[24]  J. Christian,et al.  The theory of transformations in metals and alloys , 2003 .

[25]  H. Asahina,et al.  Chemical properties of various organic electrolytes for lithium rechargeable batteries: 1. Characterization of passivating layer formed on graphite in alkyl carbonate solutions , 1997 .

[26]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[27]  Ralph E. White,et al.  Review of Models for Predicting the Cycling Performance of Lithium Ion Batteries , 2006 .

[28]  E. Peled,et al.  An Advanced Tool for the Selection of Electrolyte Components for Rechargeable Lithium Batteries , 1998 .

[29]  John B. Goodenough,et al.  AC impedance analysis of polycrystalline insertion electrodes: application to Li1−xCoO2 , 1985 .

[30]  F. Meyer Zu Heringdorf,et al.  The nucleation of pentacene thin films , 2004 .

[31]  P. Chu,et al.  Nucleation and growth of amorphous carbon film on tungsten-implanted stainless steel substrates , 2006 .

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

[33]  E. Peled,et al.  Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes , 1997 .

[34]  J. Josefowicz,et al.  Electrochemistry of Highly Ordered Pyrolytic Graphite Surface Film Formation Observed by Atomic Force Microscopy , 1997 .

[35]  M. Winter,et al.  What are batteries, fuel cells, and supercapacitors? , 2004, Chemical reviews.

[36]  John Newman,et al.  A Mathematical Model for the Lithium-Ion Negative Electrode Solid Electrolyte Interphase , 2004 .

[37]  J. Kerr,et al.  Chemical reactivity of PF{sub 5} and LiPF{sub 6} in ethylene carbonate/dimethyl carbonate solutions , 2001 .

[38]  J. Yamaki,et al.  The cathodic decomposition of propylene carbonate in lithium batteries , 1987 .

[39]  Daniel Zwillinger,et al.  CRC standard mathematical tables and formulae; 30th edition , 1995 .

[40]  T. Abe,et al.  Intercalation of lithium into natural graphite flakes and heat-treated polyimide films in ether-type solvents by chemical method , 1997 .

[41]  J. P. Badiali,et al.  Passivation of a Lithium Anode - A Simulation-Model , 1996 .

[42]  S. Cheng,et al.  Enhanced growth of CoSi2 thin films on (0 0 1)Si with Co/Au/Co sandwich structures , 2008 .

[43]  H. Möhwald,et al.  Electronic conductivity and structure of DMSO-solvated A+ - and NR4+-graphite intercalation compounds , 1980 .

[44]  J. Yamaki,et al.  Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells , 2002 .

[45]  Liquan Chen,et al.  Ag-enhanced SEI formation on Si particles for lithium batteries , 2003 .