Quantifying Graphite Solid-Electrolyte Interphase Chemistry and its Impact on Fast Charging

McShane, Eric J.; Bergstrom, Helen K.; Weddle, Peter J.; Brown, David E.; Colclasure, Andrew M.; McCloskey, Bryan D.

doi:10.1021/acsenergylett.2c01059

Quantifying Graphite Solid-Electrolyte Interphase Chemistry and its Impact on Fast Charging

Journal Article · Mon Jul 25 00:00:00 EDT 2022 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.2c01059· OSTI ID:1879455

^[1]; ^[1]; Weddle, Peter J. ^[2]; Brown, David E. ^[1]; ^[2]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

The solid-electrolyte interphase (SEI) enables the remarkable capacity retention of lithium-ion batteries, yet a comprehensive quantitative description of the SEI composition remains elusive. Using a combination of differential electrochemical mass spectrometry and mass spectrometry titration, we quantify graphite SEI components formed under electrolytes of varying salt concentrations. We find that, regardless of salt concentration, a conversion of initially deposited lithium ethylene dicarbonate to monocarbonates (likely lithium ethylene monocarbonate) and noncarbonate species occurs, and the extent of this conversion increases with electrolyte aging. Here, we additionally demonstrate that as the concentration increases (up to 2.0 M LiPF6), the SEI becomes progressively thinner with more LiF and less solid carbonates deposited. Finally, we reveal that less dead lithium formation and less solid carbonate deposition occur during prolonged fast charging for higher-concentration electrolytes. Because of the advantages imparted by a thinner SEI, the onset state of charge for lithium plating for the 2.0 M electrolyte is later than that predicted by a standard electrochemical model, underscoring the importance of explicit SEI effects in future electrochemical models.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office, Applied Battery Research and Extreme Fast Charge Program (XCEL); National Science Foundation Graduate Research Fellowship Program (NSFGRFP)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1879455

Report Number(s):: NREL/JA-5700-80769; MainId:77553; UUID:e5cabdfe-6358-4399-a42c-b7bce0cecbfb; MainAdminID:64947

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 7; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries Zhang, Xue-Qiang; Cheng, Xin-Bing; Chen, Xiang Advanced Functional Materials, Vol. 27, Issue 10 https://doi.org/10.1002/adfm.201605989	journal	January 2017
Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander Advanced Science, Vol. 4, Issue 8 https://doi.org/10.1002/advs.201700032	journal	March 2017
The behaviour of lithium electrodes in propylene and ethylene carbonate: Te major factors that influence Li cycling efficiency Aurbach, Doron; Gofer, Yosef; Ben-Zion, Moshe Journal of Electroanalytical Chemistry, Vol. 339, Issue 1-2 https://doi.org/10.1016/0022-0728(92)80467-I	journal	November 1992
An analysis of rechargeable lithium-ion batteries after prolonged cycling Aurbach, Doron; Markovsky, Boris; Rodkin, Alexander Electrochimica Acta, Vol. 47, Issue 12 https://doi.org/10.1016/S0013-4686(02)00013-0	journal	May 2002
DEMS study of gas evolution at thick graphite electrodes for lithium-ion batteries: the effect of γ-butyrolactone Lanz, Martin; Novák, Petr Journal of Power Sources, Vol. 102, Issue 1-2 https://doi.org/10.1016/S0378-7753(01)00826-6	journal	December 2001
Electrochemically lithiated graphite characterised by photoelectron spectroscopy Andersson, A. M.; Henningson, A.; Siegbahn, H. Journal of Power Sources, Vol. 119-121 https://doi.org/10.1016/S0378-7753(03)00277-5	journal	June 2003
FTIR and DEMS investigations on the electroreduction of chloroethylene carbonate-based electrolyte solutions for lithium-ion cells Winter, M.; Imhof, R.; Joho, F. Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/S0378-7753(99)00116-0	journal	September 1999
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Electrode scale and electrolyte transport effects on extreme fast charging of lithium-ion cells Colclasure, Andrew M.; Tanim, Tanvir R.; Jansen, Andrew N. Electrochimica Acta, Vol. 337 https://doi.org/10.1016/j.electacta.2020.135854	journal	March 2020
Generation and Evolution of the Solid Electrolyte Interphase of Lithium-Ion Batteries Heiskanen, Satu Kristiina; Kim, Jongjung; Lucht, Brett L. Joule, Vol. 3, Issue 10 https://doi.org/10.1016/j.joule.2019.08.018	journal	October 2019
SEI film formation on highly crystalline graphitic materials in lithium-ion batteries Buqa, H.; Würsig, A.; Vetter, J. Journal of Power Sources, Vol. 153, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.05.036	journal	February 2006
TG-MS analysis of solid electrolyte interphase (SEI) on graphite negative-electrode in lithium-ion batteries Zhao, Liwei; Watanabe, Izumi; Doi, Takayuki Journal of Power Sources, Vol. 161, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.05.045	journal	October 2006
In situ detection of lithium metal plating on graphite in experimental cells Uhlmann, C.; Illig, J.; Ender, M. Journal of Power Sources, Vol. 279 https://doi.org/10.1016/j.jpowsour.2015.01.046	journal	April 2015
High accuracy in-situ direct gas analysis of Li-ion batteries Geng, Linxiao; Wood, David L.; Lewis, Samuel A. Journal of Power Sources, Vol. 466 https://doi.org/10.1016/j.jpowsour.2020.228211	journal	August 2020
Operando investigation of the solid electrolyte interphase mechanical and transport properties formed from vinylene carbonate and fluoroethylene carbonate Kitz, Paul G.; Lacey, Matthew J.; Novák, Petr Journal of Power Sources, Vol. 477 https://doi.org/10.1016/j.jpowsour.2020.228567	journal	November 2020
Detecting onset of lithium plating during fast charging of Li-ion batteries using operando electrochemical impedance spectroscopy Brown, David E.; McShane, Eric J.; Konz, Zachary M. Cell Reports Physical Science, Vol. 2, Issue 10 https://doi.org/10.1016/j.xcrp.2021.100589	journal	October 2021
Toward Unraveling the Origin of Lithium Fluoride in the Solid Electrolyte Interphase Cao, Chuntian; Pollard, Travis P.; Borodin, Oleg Chemistry of Materials, Vol. 33, Issue 18 https://doi.org/10.1021/acs.chemmater.1c01744	journal	September 2021
Lithium-Ion Model Behavior in an Ethylene Carbonate Electrolyte Using Molecular Dynamics Kumar, Narendra; Seminario, Jorge M. The Journal of Physical Chemistry C, Vol. 120, Issue 30 https://doi.org/10.1021/acs.jpcc.6b03709	journal	July 2016
Oxidation of Ethylene Carbonate on Li Metal Oxide Surfaces Østergaard, Thomas M.; Giordano, Livia; Castelli, Ivano E. The Journal of Physical Chemistry C, Vol. 122, Issue 19 https://doi.org/10.1021/acs.jpcc.8b01713	journal	April 2018
Hydrolysis of LiPF ₆ in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous Media Stich, Michael; Göttlinger, Mara; Kurniawan, Mario The Journal of Physical Chemistry C, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcc.8b02080	journal	April 2018
Coupled LiPF ₆ Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries Yu, Yang; Karayaylali, Pinar; Katayama, Yu The Journal of Physical Chemistry C, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpcc.8b07848	journal	October 2018
In Situ/ex Situ Investigations on the Formation of the Mosaic Solid Electrolyte Interface Layer on Graphite Anode for Lithium-Ion Batteries Rikka, Vallabha Rao; Sahu, Sumit Ranjan; Chatterjee, Abhijit The Journal of Physical Chemistry C, Vol. 122, Issue 50 https://doi.org/10.1021/acs.jpcc.8b09210	journal	November 2018
Evolution of the Solid–Electrolyte Interphase on Carbonaceous Anodes Visualized by Atomic-Resolution Cryogenic Electron Microscopy Huang, William; Attia, Peter M.; Wang, Hansen Nano Letters, Vol. 19, Issue 8 https://doi.org/10.1021/acs.nanolett.9b01515	journal	July 2019
Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells Fonseca Rodrigues, Marco-Tulio; Maroni, Victor A.; Gosztola, David J. ACS Applied Energy Materials, Vol. 2, Issue 1 https://doi.org/10.1021/acsaem.8b01975	journal	December 2018
Influence of Water Contamination on the SEI Formation in Li-Ion Cells: An Operando EQCM-D Study Kitz, Paul G.; Novák, Petr; Berg, Erik J. ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.0c01642	journal	March 2020
Detecting the Onset of Lithium Plating and Monitoring Fast Charging Performance with Voltage Relaxation Konz, Zachary M.; McShane, Eric J.; McCloskey, Bryan D. ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00831	journal	May 2020
Quantification of Inactive Lithium and Solid–Electrolyte Interphase Species on Graphite Electrodes after Fast Charging McShane, Eric J.; Colclasure, Andrew M.; Brown, David E. ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00859	journal	May 2020
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate Wang, Yixuan; Nakamura, Shinichiro; Ue, Makoto Journal of the American Chemical Society, Vol. 123, Issue 47 https://doi.org/10.1021/ja0164529	journal	November 2001
Lithium Ethylene Dicarbonate Identified as the Primary Product of Chemical and Electrochemical Reduction of EC in 1.2 M LiPF ₆ /EC:EMC Electrolyte Zhuang, Guorong V.; Xu, Kang; Yang, Hui The Journal of Physical Chemistry B, Vol. 109, Issue 37 https://doi.org/10.1021/jp052474w	journal	September 2005
Syntheses and Characterization of Lithium Alkyl Mono- and Dicarbonates as Components of Surface Films in Li-Ion Batteries Xu, Kang; Zhuang, Guorong V.; Allen, Jan L. The Journal of Physical Chemistry B, Vol. 110, Issue 15 https://doi.org/10.1021/jp0601522	journal	March 2006
Lithium Ion Battery Graphite Solid Electrolyte Interphase Revealed by Microscopy and Spectroscopy Nie, Mengyun; Chalasani, Dinesh; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 117, Issue 3, p. 1257-1267 https://doi.org/10.1021/jp3118055	journal	January 2013
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry McCloskey, B. D.; Bethune, D. S.; Shelby, R. M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166 https://doi.org/10.1021/jz200352v	journal	May 2011
Interface Investigations of a Commercial Lithium Ion Battery Graphite Anode Material by Sputter Depth Profile X-ray Photoelectron Spectroscopy Niehoff, Philip; Passerini, Stefano; Winter, Martin Langmuir, Vol. 29, Issue 19 https://doi.org/10.1021/la400764r	journal	April 2013
Identifying the components of the solid–electrolyte interphase in Li-ion batteries Wang, Luning; Menakath, Anjali; Han, Fudong Nature Chemistry, Vol. 11, Issue 9 https://doi.org/10.1038/s41557-019-0304-z	journal	August 2019
In situ quantification of interphasial chemistry in Li-ion battery Liu, Tongchao; Lin, Lingpiao; Bi, Xuanxuan Nature Nanotechnology, Vol. 14, Issue 1 https://doi.org/10.1038/s41565-018-0284-y	journal	November 2018
Quantifying inactive lithium in lithium metal batteries Fang, Chengcheng; Li, Jinxing; Zhang, Minghao Nature, Vol. 572, Issue 7770 https://doi.org/10.1038/s41586-019-1481-z	journal	August 2019
Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries Strmcnik, Dusan; Castelli, Ivano E.; Connell, Justin G. Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0047-z	journal	April 2018
Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite Andersson, A. M.; Edström, K. Journal of The Electrochemical Society, Vol. 148, Issue 10 https://doi.org/10.1149/1.1397771	journal	January 2001
Analysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attentuated Total Reflection Infrared Spectroscopy Zhuang, Guorong V.; Ross, Philip N. Electrochemical and Solid-State Letters, Vol. 6, Issue 7 https://doi.org/10.1149/1.1575594	journal	January 2003
Decomposition of LiPF[sub 6] and Stability of PF[sub 5] in Li-Ion Battery Electrolytes Tasaki, Ken; Kanda, Katsuya; Nakamura, Shinichiro Journal of The Electrochemical Society, Vol. 150, Issue 12 https://doi.org/10.1149/1.1622406	journal	January 2003
Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes Peled, E. Journal of The Electrochemical Society, Vol. 144, Issue 8 https://doi.org/10.1149/1.1837858	journal	January 1997
Identification of Li Battery Electrolyte Degradation Products Through Direct Synthesis and Characterization of Alkyl Carbonate Salts Gireaud, L.; Grugeon, S.; Laruelle, S. Journal of The Electrochemical Society, Vol. 152, Issue 5 https://doi.org/10.1149/1.1872673	journal	January 2005
Reduction Reactions of Carbonate Solvents for Lithium Ion Batteries Seo, D. M.; Chalasani, D.; Parimalam, B. S. ECS Electrochemistry Letters, Vol. 3, Issue 9 https://doi.org/10.1149/2.0021409eel	journal	January 2014
Gas Evolution at Graphite Anodes Depending on Electrolyte Water Content and SEI Quality Studied by On-Line Electrochemical Mass Spectrometry Bernhard, Rebecca; Metzger, Michael; Gasteiger, Hubert A. Journal of The Electrochemical Society, Vol. 162, Issue 10 https://doi.org/10.1149/2.0191510jes	journal	January 2015
Hydrolysis of Ethylene Carbonate with Water and Hydroxide under Battery Operating Conditions Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie Journal of The Electrochemical Society, Vol. 163, Issue 7 https://doi.org/10.1149/2.0411607jes	journal	January 2016
Requirements for Enabling Extreme Fast Charging of High Energy Density Li-Ion Cells while Avoiding Lithium Plating Colclasure, Andrew M.; Dunlop, Alison R.; Trask, Stephen E. Journal of The Electrochemical Society, Vol. 166, Issue 8 https://doi.org/10.1149/2.0451908jes	journal	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
batteries
fast charge
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lithium-ion
solid-electrolyte interface (SEI)

Quantifying Graphite Solid-Electrolyte Interphase Chemistry and its Impact on Fast Charging

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