Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation

Gibson, Luke D.; Pfaendtner, Jim

doi:10.1039/d0cp03286g

Solvent oligomerization pathways facilitated by electrolyte additives during solid-electrolyte interphase formation

Journal Article · Tue Sep 01 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp03286g· OSTI ID:1776852

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Univ. of Washington, Seattle, WA (United States); University of Washington, Seattle, WA 98195
Univ. of Washington, Seattle, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

The solid–electrolyte interphase (SEI) layer formation is known to play an important role in determining the lifetime of lithium-ion batteries. A thin, stable SEI layer is linked to overall improved battery performance and longevity, however, the factors and mechanisms that lead to optimal SEI morphology and composition are not well understood. Inclusion of electrolyte additives (fluoroethylene carbonate, FEC; and vinylene carbonate, VC) is often necessary for improving SEI characteristics. To understand how these electrolyte additives impact SEI formation, we employed molecular dynamics (MD) and density functional theory (DFT) simulations to study the reaction networks and oligomerization pathways, respectively, for three systems containing ethylene carbonate (EC), a lithium ion, and FEC or VC. MD simulations suggest radical oligomerization pathways analogous to traditional oligomerization with nucleophilic alkoxide species via SN1 reaction mechanisms. Both S_N1 and S_N2 mechanisms were studied for all three systems using DFT. Oligomerization reactions were studied with both a standard alkoxide species and a ring-opened EC radical as the nucleophiles and EC, FEC, and VC as the electrophiles. For all cases, FEC and VC exhibited lower free energy barriers and more stable adducts when compared with EC. We conclude that one of the role of additives is to modify the oligomerization process of EC by introducing branching points (FEC) or termination points (VC).

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0019483

OSTI ID:: 1776852

Alternate ID(s):: OSTI ID: 1664493

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 37 Vol. 22; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Effect of Hexafluorophosphate and Fluoroethylene Carbonate on Electrochemical Performance and the Surface Layer of Hard Carbon for Sodium-Ion Batteries Dahbi, Mouad; Nakano, Takeshi; Yabuuchi, Naoaki ChemElectroChem, Vol. 3, Issue 11 https://doi.org/10.1002/celc.201600365	journal	October 2016
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni Journal of Computational Chemistry, Vol. 24, Issue 6 https://doi.org/10.1002/jcc.10189	journal	April 2003
Time-reversible always stable predictor-corrector method for molecular dynamics of polarizable molecules Kolafa, Ji?� Journal of Computational Chemistry, Vol. 25, Issue 3 https://doi.org/10.1002/jcc.10385	journal	January 2003
Performance of density functionals for calculation of reductive ring-opening reaction energies of Li + -EC and Li + -VC Han, Young-Kyu; Lee, Ssang Uck Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 112, Issue 2 https://doi.org/10.1007/s00214-004-0572-5	journal	May 2004
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements Stewart, James J. P. Journal of Molecular Modeling, Vol. 13, Issue 12 https://doi.org/10.1007/s00894-007-0233-4	journal	September 2007
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries Aurbach, Doron Journal of Power Sources, Vol. 89, Issue 2 https://doi.org/10.1016/S0378-7753(00)00431-6	journal	August 2000
PLUMED 2: New feathers for an old bird Tribello, Gareth A.; Bonomi, Massimiliano; Branduardi, Davide Computer Physics Communications, Vol. 185, Issue 2 https://doi.org/10.1016/j.cpc.2013.09.018	journal	February 2014
Importance of Reduction and Oxidation Stability of High Voltage Electrolytes and Additives Delp, Samuel A.; Borodin, Oleg; Olguin, Marco Electrochimica Acta, Vol. 209 https://doi.org/10.1016/j.electacta.2016.05.100	journal	August 2016
Theoretical evaluation of ethylene carbonate anion transport and its impact on solid electrolyte interphase formation Boyer, Mathew J.; Hwang, Gyeong S. Electrochimica Acta, Vol. 266 https://doi.org/10.1016/j.electacta.2018.02.045	journal	March 2018
Synthesis and electrochemical performance of doped LiCoO2 materials Needham, S. A.; Wang, G. X.; Liu, H. K. Journal of Power Sources, Vol. 174, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.06.228	journal	December 2007
Effect of electrolytes on the structure and evolution of the solid electrolyte interphase (SEI) in Li-ion batteries: A molecular dynamics study Kim, Sang-Pil; Duin, Adri C. T. van; Shenoy, Vivek B. Journal of Power Sources, Vol. 196, Issue 20 https://doi.org/10.1016/j.jpowsour.2011.05.061	journal	October 2011
Sparse matrix multiplication: The distributed block-compressed sparse row library Borštnik, Urban; VandeVondele, Joost; Weber, Valéry Parallel Computing, Vol. 40, Issue 5-6 https://doi.org/10.1016/j.parco.2014.03.012	journal	May 2014
Computational Exploration of the Li-Electrode\|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer Li, Yunsong; Leung, Kevin; Qi, Yue Accounts of Chemical Research, Vol. 49, Issue 10 https://doi.org/10.1021/acs.accounts.6b00363	journal	September 2016
Fundamental Mechanisms of Solvent Decomposition Involved in Solid-Electrolyte Interphase Formation in Sodium Ion Batteries Kumar, Hemant; Detsi, Eric; Abraham, Daniel P. Chemistry of Materials, Vol. 28, Issue 24 https://doi.org/10.1021/acs.chemmater.6b03403	journal	December 2016
Identification of Electrolyte-Soluble Organic Cross-Talk Species in a Lithium-Ion Battery via a Two-Compartment Cell Sahore, Ritu; Dogan, Fulya; Bloom, Ira D. Chemistry of Materials, Vol. 31, Issue 8 https://doi.org/10.1021/acs.chemmater.9b00063	journal	March 2019
Reaction Product Analysis of the Most Active “Inactive” Material in Lithium-Ion Batteries—The Electrolyte. II: Battery Operation and Additive Impact Henschel, Jonas; Peschel, Christoph; Günter, Florian Chemistry of Materials, Vol. 31, Issue 24 https://doi.org/10.1021/acs.chemmater.9b04135	journal	November 2019
Automated Discovery and Refinement of Reactive Molecular Dynamics Pathways Wang, Lee-Ping; McGibbon, Robert T.; Pande, Vijay S. Journal of Chemical Theory and Computation, Vol. 12, Issue 2 https://doi.org/10.1021/acs.jctc.5b00830	journal	January 2016
Efficient Sampling of High-Dimensional Free-Energy Landscapes with Parallel Bias Metadynamics Pfaendtner, Jim; Bonomi, Massimiliano Journal of Chemical Theory and Computation, Vol. 11, Issue 11 https://doi.org/10.1021/acs.jctc.5b00846	journal	October 2015
Lifting the Curse of Dimensionality on Enhanced Sampling of Reaction Networks with Parallel Bias Metadynamics Fu, Christopher D.; Pfaendtner, Jim Journal of Chemical Theory and Computation, Vol. 14, Issue 5 https://doi.org/10.1021/acs.jctc.7b01289	journal	March 2018
What Makes Fluoroethylene Carbonate Different? Shkrob, Ilya A.; Wishart, James F.; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b03591	journal	June 2015
A Computational Chemical Insight into Microscopic Additive Effect on Solid Electrolyte Interphase Film Formation in Sodium-Ion Batteries: Suppression of Unstable Film Growth by Intact Fluoroethylene Carbonate Takenaka, Norio; Sakai, Hirofumi; Suzuki, Yuichi The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b04206	journal	July 2015
Degradation of Ethylene Carbonate Electrolytes of Lithium Ion Batteries via Ring Opening Activated by LiCoO ₂ Cathode Surfaces and Electrolyte Species Tebbe, Jonathon L.; Fuerst, Thomas F.; Musgrave, Charles B. ACS Applied Materials & Interfaces, Vol. 8, Issue 40 https://doi.org/10.1021/acsami.6b06157	journal	September 2016
Ab Initio Modeling of Electrolyte Molecule Ethylene Carbonate Decomposition Reaction on Li(Ni,Mn,Co)O ₂ Cathode Surface Xu, Shenzhen; Luo, Guangfu; Jacobs, Ryan ACS Applied Materials & Interfaces, Vol. 9, Issue 24 https://doi.org/10.1021/acsami.7b03435	journal	June 2017
Concentration Effect of Fluoroethylene Carbonate on the Formation of Solid Electrolyte Interphase Layer in Sodium-Ion Batteries Bouibes, Amine; Takenaka, Norio; Fujie, Takuya ACS Applied Materials & Interfaces, Vol. 10, Issue 34 https://doi.org/10.1021/acsami.8b07530	journal	August 2018
Identification of the Solid Electrolyte Interface on the Si/C Composite Anode with FEC as the Additive Li, Qi; Liu, Xiangsi; Han, Xiang ACS Applied Materials & Interfaces, Vol. 11, Issue 15 https://doi.org/10.1021/acsami.8b22221	journal	February 2019
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
Additive Effect on Reductive Decomposition and Binding of Carbonate-Based Solvent toward Solid Electrolyte Interphase Formation in Lithium-Ion Battery Ushirogata, Keisuke; Sodeyama, Keitaro; Okuno, Yukihiro Journal of the American Chemical Society, Vol. 135, Issue 32 https://doi.org/10.1021/ja405079s	journal	July 2013
Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate Jin, Yanting; Kneusels, Nis-Julian H.; Magusin, Pieter C. M. M. Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b06834	journal	October 2017
Understanding Fluoroethylene Carbonate and Vinylene Carbonate Based Electrolytes for Si Anodes in Lithium Ion Batteries with NMR Spectroscopy Jin, Yanting; Kneusels, Nis-Julian H.; Marbella, Lauren E. Journal of the American Chemical Society, Vol. 140, Issue 31 https://doi.org/10.1021/jacs.8b03408	journal	July 2018
Theoretical Insights into the Reductive Decompositions of Propylene Carbonate and Vinylene Carbonate: Density Functional Theory Studies Wang, Yixuan; Balbuena, Perla B. The Journal of Physical Chemistry B, Vol. 106, Issue 17 https://doi.org/10.1021/jp014371t	journal	May 2002
Solvent Decompositions and Physical Properties of Decomposition Compounds in Li-Ion Battery Electrolytes Studied by DFT Calculations and Molecular Dynamics Simulations Tasaki, Ken The Journal of Physical Chemistry B, Vol. 109, Issue 7 https://doi.org/10.1021/jp047240b	journal	February 2005
Molecular Dynamics Simulations of Lithium Alkyl Carbonates Borodin, Oleg; Smith, Grant D.; Fan, Peng The Journal of Physical Chemistry B, Vol. 110, Issue 45 https://doi.org/10.1021/jp0639142	journal	November 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
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 117, Issue 38, p. 19270-19279 https://doi.org/10.1021/jp406273p	journal	September 2013
Car–Parrinello Molecular Dynamics + Metadynamics Study of High-Temperature Methanol Oxidation Reactions Using Generic Collective Variables Zheng, Shaohui; Pfaendtner, Jim The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp500398k	journal	May 2014
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
Understanding the physical metallurgy of the CoCrFeMnNi high-entropy alloy: an atomistic simulation study Choi, Won-Mi; Jo, Yong Hee; Sohn, Seok Su npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-017-0060-9	journal	January 2018
Decomposition of the fluoroethylene carbonate additive and the glue effect of lithium fluoride products for the solid electrolyte interphase: an ab initio study Okuno, Yukihiro; Ushirogata, Keisuke; Sodeyama, Keitaro Physical Chemistry Chemical Physics, Vol. 18, Issue 12 https://doi.org/10.1039/C5CP07583A	journal	January 2016
Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes Leung, Kevin; Budzien, Joanne L. Physical Chemistry Chemical Physics, Vol. 12, Issue 25 https://doi.org/10.1039/b925853a	journal	January 2010
An efficient orbital transformation method for electronic structure calculations VandeVondele, Joost; Hutter, Jürg The Journal of Chemical Physics, Vol. 118, Issue 10 https://doi.org/10.1063/1.1543154	journal	March 2003
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
A molecular dynamics method for simulations in the canonical ensemble NosÉ, SH[Ubar]ICHI Molecular Physics, Vol. 100, Issue 1 https://doi.org/10.1080/00268970110089108	journal	January 2002
Enhanced sampling of chemical and biochemical reactions with metadynamics Zheng, Shaohui; Pfaendtner, Jim Molecular Simulation, Vol. 41, Issue 1-3 https://doi.org/10.1080/08927022.2014.923574	journal	June 2014
Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method Barducci, Alessandro; Bussi, Giovanni; Parrinello, Michele Physical Review Letters, Vol. 100, Issue 2 https://doi.org/10.1103/PhysRevLett.100.020603	journal	January 2008
Graph Theory Meets Ab Initio Molecular Dynamics: Atomic Structures and Transformations at the Nanoscale Pietrucci, Fabio; Andreoni, Wanda Physical Review Letters, Vol. 107, Issue 8 https://doi.org/10.1103/PhysRevLett.107.085504	journal	August 2011
The Design and Implementation of FFTW3 Frigo, M.; Johnson, S. G. Proceedings of the IEEE, Vol. 93, Issue 2 https://doi.org/10.1109/JPROC.2004.840301	journal	February 2005
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy Li, Yuzhang; Li, Yanbin; Pei, Allen Science, Vol. 358, Issue 6362 https://doi.org/10.1126/science.aam6014	journal	October 2017
Enhancing Important Fluctuations: Rare Events and Metadynamics from a Conceptual Viewpoint Valsson, Omar; Tiwary, Pratyush; Parrinello, Michele Annual Review of Physical Chemistry, Vol. 67, Issue 1 https://doi.org/10.1146/annurev-physchem-040215-112229	journal	May 2016
Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions Sloop, S. E.; Pugh, J. K.; Wang, S. Electrochemical and Solid-State Letters, Vol. 4, Issue 4 https://doi.org/10.1149/1.1353158	journal	January 2001
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
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures Aurbach, D. Journal of The Electrochemical Society, Vol. 143, Issue 12 https://doi.org/10.1149/1.1837300	journal	January 1996
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries Arora, Pankaj; White, Ralph E.; Doyle, Marc Journal of The Electrochemical Society, Vol. 145, Issue 10, p. 3647-3667 https://doi.org/10.1149/1.1838857	journal	January 1998
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model Peled, E. Journal of The Electrochemical Society, Vol. 126, Issue 12 https://doi.org/10.1149/1.2128859	journal	January 1979
Identification of the Source of Evolved Gas in Li-Ion Batteries Using [sup 13]C-labeled Solvents Onuki, Masamichi; Kinoshita, Shinichi; Sakata, Yuuichi Journal of The Electrochemical Society, Vol. 155, Issue 11 https://doi.org/10.1149/1.2969947	journal	January 2008
A Comparative Study of Vinylene Carbonate and Fluoroethylene Carbonate Additives for LiCoO ₂ /Graphite Pouch Cells Wang, David Yaohui; Sinha, N. N.; Burns, J. C. Journal of The Electrochemical Society, Vol. 161, Issue 4 https://doi.org/10.1149/2.001404jes	journal	January 2014
Near-Shore Aggregation Mechanism of Electrolyte Decomposition Products to Explain Solid Electrolyte Interphase Formation Ushirogata, Keisuke; Sodeyama, Keitaro; Futera, Zdenek Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0301514jes	journal	January 2015
Impact of Chemical Follow-up Reactions for Lithium Ion Electrolytes: Generation of Nucleophilic Species, Solid Electrolyte Interphase, and Gas Formation Burkhardt, Stephen E. Journal of The Electrochemical Society, Vol. 164, Issue 4 https://doi.org/10.1149/2.0621704jes	journal	January 2017
The Impact of CO ₂ Evolved from VC and FEC during Formation of Graphite Anodes in Lithium-Ion Batteries Schwenke, K. Uta; Solchenbach, Sophie; Demeaux, Julien Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0821910jes	journal	January 2019
Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries Leung, Kevin; Rempe, Susan B.; Foster, Michael E. Journal of The Electrochemical Society, Vol. 161, Issue 3 https://doi.org/10.1149/2.092401jes	journal	December 2013

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