Spectroscopic Compositional Analysis of Electrolyte during Initial SEI Layer Formation

The energy density of an electrochemical capacitor can be significantly improved by utilizing a lithiated negative electrode and a high surface area positive electrode. During lithiation of the negative carbon electrode, the electrolyte reacts with the electrode surface and undergoes decomposition to form a solid electrolyte interphase (SEI) layer that passivates the surface of the carbon electrode from further reactions between Li and the electrolyte. The reduction reactions that the solvent undergoes not only form insoluble and gaseous byproducts but also electrolyte-soluble products. In this work, those liquid-phase products generated by reductive decomposition of a carbonate-based electrolyte, 1.2 M LiPF6 in EC/PC/DEC (3:1:4), were analyzed at different stages during the lithiation process of an amorphous carbon electrode. An LCMS analysis of the electrolyte during the initial lithiation process was correlated to a DRIFTS analysis of the carbon electrode surface and the results from the EIS and gas-ph...

[1]  B. Conway.  Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications , 1999 .

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

[3]  Doron Aurbach,et al.  Revisiting LiClO4 as an Electrolyte for Rechargeable Lithium-Ion Batteries , 2010 .

[4]  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.

[5]  D. Aurbach,et al.  IDENTIFICATION OF SURFACE FILMS ON ELECTRODES IN NON-AQUEOUS ELECTROLYTE SOLUTIONS: SPECTROSCOPIC, ELECTRONIC AND MORPHOLOGICAL STUDIES , 2004 .

[6]  Patricia H. Smith,et al.  In situ electrochemical-mass spectroscopic investigation of solid electrolyte interphase formation on the surface of a carbon electrode , 2013 .

[7]  Martin Strohalm,et al.  mMass data miner: an open source alternative for mass spectrometric data analysis. , 2008, Rapid communications in mass spectrometry : RCM.

[8]  Martin Winter,et al.  Electrochemical double layer capacitor and lithium-ion capacitor based on carbon black , 2011 .

[9]  D. Aurbach,et al.  The Correlation Between the Surface Chemistry and the Performance of Li‐Carbon Intercalation Anodes for Rechargeable ‘Rocking‐Chair’ Type Batteries , 1994 .

[10]  Tao Zheng,et al.  An Asymmetric Hybrid Nonaqueous Energy Storage Cell , 2001 .

[11]  Dmitry Bedrov,et al.  Reactions of singly-reduced ethylene carbonate in lithium battery electrolytes: a molecular dynamics simulation study using the ReaxFF. , 2012, The journal of physical chemistry. A.

[12]  Martin Strohalm,et al.  mMass 3: a cross-platform software environment for precise analysis of mass spectrometric data. , 2010, Analytical chemistry.

[13]  D. Aurbach,et al.  Comparison Between the Electrochemical Behavior of Disordered Carbons and Graphite Electrodes in Connection with Their Structure , 2001 .

[14]  D. Aurbach,et al.  New insights into the interactions between electrode materials and electrolyte solutions for advanced nonaqueous batteries , 1999 .

[15]  Liquan Chen,et al.  SPECTROSCOPIC STUDIES OF SOLID-ELECTROLYTE INTERPHASE ON POSITIVE AND NEGATIVE ELECTRODES FOR LITHIUM ION BATTERIES , 2004 .

[16]  Y. Takeda,et al.  Carbon as negative electrodes in lithium secondary cells , 1989 .

[17]  R. Mannhold,et al.  Calculation of molecular lipophilicity: state of the art and comparison of methods on more than 96000 compounds , 2009, Journal of pharmaceutical sciences.

[18]  Yury Gogotsi,et al.  Charge storage mechanism in nanoporous carbons and its consequence for electrical double layer capacitors , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[19]  Doron Aurbach,et al.  Impedance spectroscopy of lithium and nickel electrodes in propylene carbonate solutions of different lithium salts A comparative study , 1995 .

[20]  F. Béguin,et al.  High-energy density graphite/AC capacitor in organic electrolyte , 2008 .

[21]  S. Pyun,et al.  Critical assessment of a new in situ spectroelectrochemical cell designed for the study of interfacial reactions between a porous graphite anode and alkyl carbonate solution , 2003 .

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

[23]  K. Tasaki,et al.  Solvent decompositions and physical properties of decomposition compounds in Li-ion battery electrolytes studied by DFT calculations and molecular dynamics simulations. , 2005, The journal of physical chemistry. B.

[24]  Yongyao Xia,et al.  A Hybrid Electrochemical Supercapacitor Based on a 5 V Li-Ion Battery Cathode and Active Carbon , 2005 .

[25]  S. Moon,et al.  Intercalation of lithium ions into graphite electrodes studied by AC impedance measurements , 1999 .

[26]  Petr Novák,et al.  In Situ Investigation of the Electrochemical Reduction of Carbonate Electrolyte Solutions at Graphite Electrodes , 1998 .

[27]  F. E. Little,et al.  Electrochemical impedance study of initial lithium ion intercalation into graphite powders , 2001 .

[28]  Perla B. Balbuena,et al.  Theoretical insights into the reductive decompositions of propylene carbonate and vinylene carbonate: Density functional theory studies , 2002 .

[29]  Jim P. Zheng,et al.  High energy and high power density electrochemical capacitors , 1996 .

[30]  Marcin Wojdyr,et al.  Fityk: a general-purpose peak fitting program , 2010 .

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

[32]  D. Aurbach,et al.  The Study of Surface Films Formed on Lithium and Noble Metal Electrodes in Polar Aprotic Systems By the Use of In Situ Fourier Transform Infrared Spectroscopy , 1993 .

[33]  M. Lain,et al.  A lithium ion cell containing a non-lithiated cathode , 2005 .

[34]  A. Ghose,et al.  Prediction of Hydrophobic (Lipophilic) Properties of Small Organic Molecules Using Fragmental Methods: An Analysis of ALOGP and CLOGP Methods , 1998 .

[35]  Matej Oresic,et al.  MZmine 2: Modular framework for processing, visualizing, and analyzing mass spectrometry-based molecular profile data , 2010, BMC Bioinformatics.

[36]  Diana Golodnitsky,et al.  SEI ON LITHIUM, GRAPHITE, DISORDERED CARBONS AND TIN-BASED ALLOYS , 2004 .

[37]  D. Billaud,et al.  Electroreduction of graphite in LiClO4-ethylene carbonate electrolyte. Characterization of the passivating layer by transmission electron microscopy and Fourier-transform infrared spectroscopy , 1996 .

[38]  Liquan Chen,et al.  Performance Improvement of Surface-Modified LiCoO2 Cathode Materials: An Infrared Absorption and X-Ray Photoelectron Spectroscopic Investigation , 2003 .

[39]  L. Lai,et al.  Calculating partition coefficient by atom-additive method , 2000 .

[40]  D. Aurbach,et al.  Investigation of the electrochemical windows of aprotic alkali metal (Li, Na, K) salt solutions , 2001 .

[41]  Diana Golodnitsky,et al.  Effect of carbon substrate on SEI composition and morphology , 2004 .

[42]  E. Peled,et al.  XPS analysis of the SEI formed on carbonaceous materials , 2004 .

[43]  D. Aurbach,et al.  X-ray photoelectron spectroscopy study of surface films formed on Li electrodes freshly prepared in alkyl carbonate solutions , 1999 .

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

[45]  Matej Oresic,et al.  MZmine: toolbox for processing and visualization of mass spectrometry based molecular profile data , 2006, Bioinform..

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

[47]  Jim P. Zheng,et al.  The Limitations of Energy Density for Electrochemical Capacitors , 1997 .

[48]  Sylvie Grugeon,et al.  Deciphering the multi-step degradation mechanisms of carbonate-based electrolyte in Li batteries , 2008 .

[49]  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 .

[50]  Yusaku Isobe,et al.  High-rate nano-crystalline Li4Ti5O12 attached on carbon nano-fibers for hybrid supercapacitors , 2010 .

[51]  Doron Aurbach,et al.  On the Study of Electrolyte Solutions for Li-Ion Batteries That Can Work Over a Wide Temperature Range , 2010 .

[52]  Per Jacobsson,et al.  Reactivity of lithium battery electrode materials toward non-aqueous electrolytes: spontaneous reactions at the electrode-electrolyte interface investigated by FTIR , 2001 .

[53]  E. Barsoukov,et al.  Effect of Low‐Temperature Conditions on Passive Layer Growth on Li Intercalation Materials In Situ Impedance Study , 1998 .

[54]  D. Aurbach,et al.  Impedance Spectroscopy of Nonactive Metal Electrodes at Low Potentials in Propylene Carbonate Solutions A Comparison to Studies of Li Electrodes , 1994 .

[55]  Shaomeng Wang,et al.  Computer Automated log P Calculations Based on an Extended Group Contribution Approach , 1994, J. Chem. Inf. Comput. Sci..

[56]  Thomas Jiang,et al.  Lithiation of amorphous carbon negative electrode for Li ion capacitor , 2013 .

[57]  D. Aurbach,et al.  The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries I . Li Metal Anodes , 1995 .

[58]  Michikazu Hara,et al.  Structural and Kinetic Characterization of Lithium Intercalation into Carbon Anodes for Secondary Lithium Batteries , 1995 .

[59]  Petr Novák,et al.  Gas evolution in activated carbon/propylene carbonate based double-layer capacitors , 2005 .

[60]  Jianjun Li,et al.  Hard carbon/lithium composite anode materials for Li-ion batteries , 2007 .

[61]  J. Rouzaud,et al.  Correlation of the irreversible lithium capacity with the active surface area of modified carbons , 2005 .

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

[63]  J. Tarascon,et al.  Identification of Li-Based Electrolyte Degradation Products Through DEI and ESI High-Resolution Mass Spectrometry , 2004 .

[64]  T. Abe,et al.  Formation mechanism of alkyl dicarbonates in Li-ion cells , 2005 .

[65]  Doron Aurbach,et al.  The behaviour of lithium electrodes in propylene and ethylene carbonate: Te major factors that influence Li cycling efficiency , 1992 .

[66]  D. Aurbach,et al.  Methyl Propyl Carbonate: A Promising Single Solvent for Li‐Ion Battery Electrolytes , 1997 .

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