Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Data-Driven Prediction of Formation Mechanisms of Lithium Ethylene Monocarbonate with an Automated Reaction Network

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
+ Show Author Affiliations

Interfacial reactions are notoriously difficult to characterize, and robust prediction of the chemical evolution and associated functionality of the resulting surface film is one of the grand challenges of materials chemistry. The solid-electrolyte interphase (SEI), critical to Li-ion batteries (LIBs), exemplifies such a surface film, and despite decades of work, considerable controversy remains regarding the major components of the SEI as well as their formation mechanisms. Here we use a reaction network to investigate whether lithium ethylene monocarbonate (LEMC) or lithium ethylene dicarbonate (LEDC) is the major organic component of the LIB SEI. Our data-driven, automated methodology is based on a systematic generation of relevant species using a general fragmentation/recombination procedure which provides the basis for a vast thermodynamic reaction landscape, calculated with density functional theory. The shortest pathfinding algorithms are employed to explore the reaction landscape and obtain previously proposed formation mechanisms of LEMC as well as several new reaction pathways and intermediates. For example, we identify two novel LEMC formation mechanisms: one which involves LiH generation and another that involves breaking the (CH2)O-C(=O)OLi bond in LEDC. Most importantly, we find that all identified paths, which are also kinetically favorable under the explored conditions, require water as a reactant. This condition severely limits the amount of LEMC that can form, as compared with LEDC, a conclusion that has direct impact on the SEI formation in Li-ion energy storage systems. Finally, the data-driven framework presented here is generally applicable to any electrochemical system and expected to improve our understanding of surface passivation.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Institutes of Health (NIH); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1825253
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 143; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (100)

Recent Progress in Understanding Solid Electrolyte Interphase on Lithium Metal Anodes journal December 2020
Chemical Recognition of Active Oxygen Species on the Surface of Oxygen Evolution Reaction Electrocatalysts journal June 2017
Autonomous discovery in the chemical sciences part I: Progress journal September 2019
Integrated Modeling Program, Applied Chemical Theory (IMPACT) journal January 2005
Automated discovery of chemically reasonable elementary reaction steps journal March 2013
An automated method to find transition states using chemical dynamics simulations journal November 2014
tsscds2018: A code for automated discovery of chemical reaction mechanisms and solving the kinetics journal June 2018
Traversing Dense Networks of Elementary Chemical Reactions to Predict Minimum‐Energy Reaction Mechanisms journal December 2019
Artificial Force Induced Reaction (AFIR) Method for Exploring Quantum Chemical Potential Energy Surfaces journal June 2016
Methods for exploring reaction space in molecular systems: Exploring reaction space in molecular systems
  • Dewyer, Amanda L.; Argüelles, Alonso J.; Zimmerman, Paul M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 2 https://doi.org/10.1002/wcms.1354
journal November 2017
Role of hydrogen bonds in acid-catalyzed hydrolyses of esters journal August 2011
The “absolute” electrode potential—the end of the story journal January 1990
The behaviour of lithium electrodes in propylene and ethylene carbonate: Te major factors that influence Li cycling efficiency journal November 1992
Electrochemically lithiated graphite characterised by photoelectron spectroscopy journal June 2003
Composition analysis of the passive film on the carbon electrode of a lithium-ion battery with an EC-based electrolyte journal March 1998
On the possibility of LiH formation on Li surfaces in wet electrolyte solutions journal August 1999
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling journal August 2016
The Electrolyte Genome project: A big data approach in battery materials discovery journal June 2015
Two-electron reduction of ethylene carbonate: A quantum chemistry re-examination of mechanisms journal May 2013
Investigating the solid electrolyte interphase using binder-free graphite electrodes journal January 2008
Theoretical study on the reaction mechanism for the hydrolysis of esters and amides under acidic conditions journal January 2007
Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer journal September 2016
Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries journal November 2015
Voltage Dependent Solid Electrolyte Interphase Formation in Silicon Electrodes: Monitoring the Formation of Organic Decomposition Products journal December 2015
Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods journal August 2015
Heuristics-Guided Exploration of Reaction Mechanisms journal November 2015
Context-Driven Exploration of Complex Chemical Reaction Networks journal November 2017
Comprehensive Thermochemical Benchmark Set of Realistic Closed-Shell Metal Organic Reactions journal March 2018
Kinetic Selectivity of Lithium Alkyl Carbonate Formation from Combination Reactions of Ethylene Carbonate Radical Anions journal November 2020
Dielectric Constants for Quantum Chemistry and Li-Ion Batteries: Solvent Blends of Ethylene Carbonate and Ethyl Methyl Carbonate journal September 2015
Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces journal March 2016
Facilitated Dissociation of Water in the Presence of Lithium Metal at Ambient Temperature as a Requisite for Lithium–Gas Reactions journal June 2018
SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries journal June 2016
Insights Into the Origin of Life: Did It Begin from HCN and H 2 O? journal August 2019
Stereochemically Consistent Reaction Mapping and Identification of Multiple Reaction Mechanisms through Integer Linear Optimization
  • First, Eric L.; Gounaris, Chrysanthos E.; Floudas, Christodoulos A.
  • Journal of Chemical Information and Modeling, Vol. 52, Issue 1 https://doi.org/10.1021/ci200351b
journal December 2011
Electrolytes and Interphases in Li-Ion Batteries and Beyond journal October 2014
Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry journal February 2014
Algorithms and accuracy requirements for computing reaction paths by the method of steepest descent journal March 1988
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries:  Reduction Mechanisms of Ethylene Carbonate journal November 2001
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries:  How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive? journal April 2002
Using Atomic Layer Deposition to Hinder Solvent Decomposition in Lithium Ion Batteries: First-Principles Modeling and Experimental Studies journal September 2011
A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy journal February 2015
Electrolyte Oxidation Pathways in Lithium-Ion Batteries journal July 2020
Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes journal June 2016
Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods journal January 2018
Energy Barriers for Alkaline Hydrolysis of Carboxylic Acid Esters in Aqueous Solution by Reaction Field Calculations journal August 2000
Characterization of Lithium Alkyl Carbonates by X-ray Photoelectron Spectroscopy: Experimental and Theoretical Study journal August 2005
Lithium Ethylene Dicarbonate Identified as the Primary Product of Chemical and Electrochemical Reduction of EC in 1.2 M LiPF 6 /EC:EMC Electrolyte journal September 2005
Syntheses and Characterization of Lithium Alkyl Mono- and Dicarbonates as Components of Surface Films in Li-Ion Batteries journal March 2006
Lithium Ion Battery Graphite Solid Electrolyte Interphase Revealed by Microscopy and Spectroscopy journal January 2013
Molecular Dynamics Simulations and Experimental Study of Lithium Ion Transport in Dilithium Ethylene Dicarbonate journal April 2013
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes journal April 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
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 1. Spectroscopic Observations of Radical Intermediates Generated in One-Electron Reduction of Carbonates journal September 2013
Density Functional Theory Study of the Water Dissociation on Platinum Surfaces: General Trends journal February 2014
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model journal March 1998
Discovering chemistry with an ab initio nanoreactor journal November 2014
Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries journal March 2018
Identifying the components of the solid–electrolyte interphase in Li-ion batteries journal August 2019
Identification of LiH and nanocrystalline LiF in the solid–electrolyte interphase of lithium metal anodes journal January 2021
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries journal August 2018
Quantum chemical calculations of lithium-ion battery electrolyte and interphase species journal August 2021
Reaction sampling and reactivity prediction using the stochastic surface walking method journal January 2015
A unified set of experimental organometallic data used to evaluate modern theoretical methods journal January 2016
Efficient prediction of reaction paths through molecular graph and reaction network analysis journal January 2018
Reductive reactions via excess Li in mixture electrolytes of Li ion batteries: an ab initio molecular dynamics study journal January 2019
Electrochemical potential window of battery electrolytes: the HOMO–LUMO misconception journal January 2018
The role of the hydrogen evolution reaction in the solid–electrolyte interphase formation mechanism for “ Water-in-Salt ” electrolytes journal January 2018
Mechanistic study of the ATP hydrolysis reaction in dynein motor protein journal January 2020
BonDNet: a graph neural network for the prediction of bond dissociation energies for charged molecules journal January 2021
A chemically consistent graph architecture for massive reaction networks applied to solid-electrolyte interphase formation journal January 2021
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes journal January 2010
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy journal January 2014
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I journal October 1955
Property-optimized Gaussian basis sets for molecular response calculations journal October 2010
Sampling reactive pathways with random walks in chemical space: Applications to molecular dissociation and catalysis journal September 2015
Electrolyte decomposition on Li-metal surfaces from first-principles theory journal November 2016
Formamide reaction network in gas phase and solution via a unified theoretical approach: Toward a reconciliation of different prebiotic scenarios journal November 2015
Escaping free-energy minima journal September 2002
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Navigating molecular space for reaction mechanisms: an efficient, automated procedure journal March 2014
The Exploration of Chemical Reaction Networks journal April 2020
Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite journal January 2001
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures journal January 1996
A Study of Electrochemical Reduction of Ethylene and Propylene Carbonate Electrolytes on Graphite Using ATR-FTIR Spectroscopy journal January 2005
The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries journal January 1995
The Behavior of Lithium Electrodes in Mixtures of Alkyl Carbonates and Ethers journal January 1991
Identification of Surface Films Formed on Lithium in Propylene Carbonate Solutions journal January 1987
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model journal January 1979
Theoretical Studies on the Reductive Decompositions of Solvents and Additives for Lithium-Ion Batteries near Lithium Anodes journal January 2006
Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate journal January 2011
Perspective—Surface Reactions of Electrolyte with LiNi x Co y Mn z O 2 Cathodes for Lithium Ion Batteries journal June 2020
Reduction Reactions of Carbonate Solvents for Lithium Ion Batteries journal January 2014
Origin of H 2 Evolution in LIBs: H 2 O Reduction vs. Electrolyte Oxidation journal January 2016
Review—SEI: Past, Present and Future journal January 2017
The absolute electrode potential: an explanatory note (Recommendations 1986) journal January 1986
The Solid Electrolyte Interphase – The Most Important and the Least Understood Solid Electrolyte in Rechargeable Li Batteries journal December 2009

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical reactions
Genetics
Hydrolysis
Molecules
Surface chemistry