Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d0cp03286g· OSTI ID:1776852
 [1];  [2]
  1. Univ. of Washington, Seattle, WA (United States); University of Washington, Seattle, WA 98195
  2. Univ. of Washington, Seattle, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations
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 SN1 and SN2 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).
Research Organization:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
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 journal October 2016
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model journal April 2003
Time-reversible always stable predictor-corrector method for molecular dynamics of polarizable molecules journal January 2003
Performance of density functionals for calculation of reductive ring-opening reaction energies of Li + -EC and Li + -VC journal May 2004
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements journal September 2007
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries journal August 2000
PLUMED 2: New feathers for an old bird journal February 2014
Importance of Reduction and Oxidation Stability of High Voltage Electrolytes and Additives journal August 2016
Theoretical evaluation of ethylene carbonate anion transport and its impact on solid electrolyte interphase formation journal March 2018
Synthesis and electrochemical performance of doped LiCoO2 materials 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 journal October 2011
Sparse matrix multiplication: The distributed block-compressed sparse row library journal May 2014
Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer journal September 2016
Fundamental Mechanisms of Solvent Decomposition Involved in Solid-Electrolyte Interphase Formation in Sodium Ion Batteries journal December 2016
Identification of Electrolyte-Soluble Organic Cross-Talk Species in a Lithium-Ion Battery via a Two-Compartment Cell journal March 2019
Reaction Product Analysis of the Most Active “Inactive” Material in Lithium-Ion Batteries—The Electrolyte. II: Battery Operation and Additive Impact journal November 2019
Automated Discovery and Refinement of Reactive Molecular Dynamics Pathways journal January 2016
Efficient Sampling of High-Dimensional Free-Energy Landscapes with Parallel Bias Metadynamics journal October 2015
Lifting the Curse of Dimensionality on Enhanced Sampling of Reaction Networks with Parallel Bias Metadynamics journal March 2018
What Makes Fluoroethylene Carbonate Different? 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 journal July 2015
Degradation of Ethylene Carbonate Electrolytes of Lithium Ion Batteries via Ring Opening Activated by LiCoO 2 Cathode Surfaces and Electrolyte Species journal September 2016
Ab Initio Modeling of Electrolyte Molecule Ethylene Carbonate Decomposition Reaction on Li(Ni,Mn,Co)O 2 Cathode Surface journal June 2017
Concentration Effect of Fluoroethylene Carbonate on the Formation of Solid Electrolyte Interphase Layer in Sodium-Ion Batteries journal August 2018
Identification of the Solid Electrolyte Interface on the Si/C Composite Anode with FEC as the Additive journal February 2019
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries:  Reduction Mechanisms of Ethylene Carbonate journal November 2001
Additive Effect on Reductive Decomposition and Binding of Carbonate-Based Solvent toward Solid Electrolyte Interphase Formation in Lithium-Ion Battery journal July 2013
Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate journal October 2017
Understanding Fluoroethylene Carbonate and Vinylene Carbonate Based Electrolytes for Si Anodes in Lithium Ion Batteries with NMR Spectroscopy journal July 2018
Theoretical Insights into the Reductive Decompositions of Propylene Carbonate and Vinylene Carbonate:  Density Functional Theory Studies journal May 2002
Solvent Decompositions and Physical Properties of Decomposition Compounds in Li-Ion Battery Electrolytes Studied by DFT Calculations and Molecular Dynamics Simulations journal February 2005
Molecular Dynamics Simulations of Lithium Alkyl Carbonates journal November 2006
Lithium Ion Battery Graphite Solid Electrolyte Interphase Revealed by Microscopy and Spectroscopy 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 journal September 2013
Car–Parrinello Molecular Dynamics + Metadynamics Study of High-Temperature Methanol Oxidation Reactions Using Generic Collective Variables journal May 2014
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model journal March 1998
Understanding the physical metallurgy of the CoCrFeMnNi high-entropy alloy: an atomistic simulation study 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 journal January 2016
Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes journal January 2010
An efficient orbital transformation method for electronic structure calculations journal March 2003
A unified formulation of the constant temperature molecular dynamics methods journal July 1984
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A molecular dynamics method for simulations in the canonical ensemble journal January 2002
Enhanced sampling of chemical and biochemical reactions with metadynamics journal June 2014
Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method journal January 2008
Graph Theory Meets Ab Initio Molecular Dynamics: Atomic Structures and Transformations at the Nanoscale journal August 2011
The Design and Implementation of FFTW3 journal February 2005
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy journal October 2017
Enhancing Important Fluctuations: Rare Events and Metadynamics from a Conceptual Viewpoint journal May 2016
Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions journal January 2001
Decomposition of LiPF[sub 6] and Stability of PF[sub 5] in Li-Ion Battery Electrolytes journal January 2003
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures journal January 1996
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries journal January 1998
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model journal January 1979
Identification of the Source of Evolved Gas in Li-Ion Batteries Using [sup 13]C-labeled Solvents journal January 2008
A Comparative Study of Vinylene Carbonate and Fluoroethylene Carbonate Additives for LiCoO 2 /Graphite Pouch Cells journal January 2014
Near-Shore Aggregation Mechanism of Electrolyte Decomposition Products to Explain Solid Electrolyte Interphase Formation journal January 2015
Impact of Chemical Follow-up Reactions for Lithium Ion Electrolytes: Generation of Nucleophilic Species, Solid Electrolyte Interphase, and Gas Formation journal January 2017
The Impact of CO 2 Evolved from VC and FEC during Formation of Graphite Anodes in Lithium-Ion Batteries journal January 2019
Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries journal December 2013

Similar Records

Effect of Fluoroethylene Carbonate Additives on the Initial Formation of the Solid Electrolyte Interphase on an Oxygen-Functionalized Graphitic Anode in Lithium-Ion Batteries
Journal Article · Sun Feb 14 19:00:00 EST 2021 · ACS Applied Materials and Interfaces · OSTI ID:1775254
Engineering Solid Electrolyte Interphase Composition by Assessing Decomposition Pathways of Fluorinated Organic Solvents in Lithium Metal Batteries
Journal Article · Tue Apr 07 20:00:00 EDT 2020 · Journal of the Electrochemical Society · OSTI ID:1608726

Related Subjects

25 ENERGY STORAGE
molecular simulation
solid-electrolyte interphase