Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Soft X-ray absorption spectroscopy with different probe depth was employed to characterize the solid electrolyte interphases (SEIs) formed on β-Sn single crystals with two different surface orientations. Based on comparative studies of C-K, O-K, and F-K absorption spectra between the SEIs and reference samples, SEI on Sn (100) mainly consists of porous Li2CO3 species with electrolyte uptake, while SEI on Sn (001) essentially consists of LiF and organic molecules, with a small amount of –CO3 and electrolyte buried inside. Theoretical calculation suggests that Sn (001) surface is more reactive than (100), especially after air exposure. The reactive (001) surface facilitates the decomposition of LiPF6 to form a LiF layer. In contrast, SEI on (100) surface is predominately from the typical decomposition of carbonate-based electrolyte. While the LiF passivates Sn (001) electrode after one cycle, the porous carbonate layer on (100) surface does not prevent further decomposition of electrolyte after many cycles. This leads to drastically different electrochemical behavior and morphology of the two SEIs. The result is a direct proof that surface properties of active materials could strongly impact the SEI formation on electrodes even with the same electrolyte. Such effect could lead to distinct SEI formation and electrochemical performance.

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

[2]  Doron Aurbach,et al.  A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions , 2002 .

[3]  Doron Aurbach,et al.  LiPF3 ( CF 2 CF 3 ) 3 : A Salt for Rechargeable Lithium Ion Batteries , 2003 .

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

[5]  Kang Xu,et al.  Syntheses and characterization of lithium alkyl mono- and dicarbonates as components of surface films in Li-ion batteries. , 2006, The journal of physical chemistry. B.

[6]  Seung‐Wan Song,et al.  Surface layer formation on Sn anode: ATR FTIR spectroscopic characterization , 2009 .

[7]  Martin Winter,et al.  Electrochemical lithiation of tin and tin-based intermetallics and composites , 1999 .

[8]  Bruno Scrosati,et al.  Nanostructured Sn–C Composite as an Advanced Anode Material in High‐Performance Lithium‐Ion Batteries , 2007 .

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

[10]  Seung M. Oh,et al.  Passivating Ability of Surface Film Derived from Vinylene Carbonate on Tin Negative Electrode , 2011 .

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

[12]  M. Whittingham,et al.  Anodes for lithium batteries: tin revisited , 2003 .

[13]  Gerbrand Ceder,et al.  Efficient creation and convergence of surface slabs , 2013 .

[14]  Akio Kotani,et al.  Core Level Spectroscopy of Solids , 2008 .

[15]  Shuru Chen,et al.  Studies of the interfacial properties of an electroplated Sn thin film electrode/electrolyte using in situ MFTIRS and EQCM. , 2007, Langmuir : the ACS journal of surfaces and colloids.

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

[17]  Louis S Roseguo,et al.  Key electronic states in lithium battery materials probed by soft X-ray spectroscopy , 2013 .

[18]  Kristin A. Persson,et al.  Commentary: The Materials Project: A materials genome approach to accelerating materials innovation , 2013 .

[19]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[20]  Robert Kostecki,et al.  In situ AFM studies of SEI formation at a Sn electrode , 2009 .

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

[22]  Tao Zheng,et al.  Mechanisms for Lithium Insertion in Carbonaceous Materials , 1995, Science.

[23]  D. Aurbach,et al.  The Study of Surface Film Formation on Noble-Metal Electrodes in Alkyl Carbonates/Li Salt Solutions, Using Simultaneous in Situ AFM, EQCM, FTIR, and EIS , 1999 .

[24]  Kazuhisa Tamura,et al.  Dynamic structural changes at LiMn2O4/electrolyte interface during lithium battery reaction. , 2010, Journal of the American Chemical Society.

[25]  R. Qiao,et al.  Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy , 2012, PloS one.

[26]  G. Zhuang,et al.  Analysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attentuated Total Reflection Infrared Spectroscopy , 2003 .

[27]  Ulrich Dahmen,et al.  New software tools for the calculation and display of isolated and attached interfacial-energy minimizing particle shapes , 2012, Journal of Materials Science.

[28]  J. Dahn,et al.  Electrochemical and In Situ X‐Ray Diffraction Studies of the Reaction of Lithium with Tin Oxide Composites , 1997 .

[29]  J. Dahn,et al.  Anomalous, high-voltage irreversible capacity in tin electrodes for lithium batteries , 2003 .

[30]  M. Inaba,et al.  Irreversible capacity of electrodeposited Sn thin film anode , 2005 .

[31]  Noriyuki Tamura,et al.  Study on the anode behavior of Sn and Sn–Cu alloy thin-film electrodes , 2002 .

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

[33]  Diana Golodnitsky,et al.  Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies , 2001 .

[34]  D. Aurbach,et al.  Correlation between surface chemistry, morphology, cycling efficiency and interfacial properties of Li electrodes in solutions containing different Li salts , 1994 .

[35]  C. Delacourt,et al.  Effect of Manganese Contamination on the Solid-Electrolyte-Interphase Properties in Li-Ion Batteries , 2013 .

[36]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[37]  K. Edström,et al.  Solid electrolyte interphase on graphite Li-ion battery anodes studied by soft X-ray spectroscopy , 2004 .

[38]  J. Tarascon,et al.  Decomposition of ethylene carbonate on electrodeposited metal thin film anode , 2010 .

[39]  J. Stöhr,et al.  First experimental results from IBM/TENN/TULANE/LLNL/LBL undulator beamline at the advanced light source , 1995 .

[40]  T. Baumann,et al.  Surface electronic states in three-dimensional SnO2 nanostructures , 2005 .

[41]  R. Huggins.  Lithium alloy negative electrodes formed from convertible oxides , 1998 .

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

[43]  J. Goodenough.  Challenges for Rechargeable Li Batteries , 2010 .

[44]  R. V. Duyne,et al.  Wulff construction for alloy nanoparticles. , 2011, Nano letters.

[45]  R. Kostecki,et al.  Ultrafast laser induced breakdown spectroscopy of electrode/electrolyte interfaces , 2012 .

[46]  R. Kostecki,et al.  Interfacial processes at single-crystal β-Sn electrodes in organic carbonate electrolytes , 2011 .