Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate

Yu, Jiamei; Balbuena, Perla B.; Budzien, Joanne; Leung, Kevin

doi:10.1149/1.3545977

Cited by 80 publications

(141 citation statements)

References 52 publications

Supporting

Mentioning

127

Contrasting

Order By: Relevance

“…[14] We found that in the liquid state, electron attachment on to an EC -anion with a broken C E -O 1 bond leads to the breaking of additional C E -O 1 bond and the formation of CO 3 2-and C 2 H 4 fragments (see Fig. 1 for labeling) while EC reduction at a Li metal surface still favors EC decomposition to form CO similar to what was observed for the LiC 6 interface, see Figure 2.…”

Section: Ab Initio MD Of Ec/lithium Interfacessupporting

confidence: 70%

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Leung¹,

Hudak²,

Liu³

et al. 2012

Self Cite

View full text Add to dashboard Cite

We report the development of new experimental capabilities and ab initio modeling for real-time studies of Li-ion battery electrochemical reactions. We developed three capabilities for in-situ transmission electron microscopy (TEM) studies: a capability that uses a nanomanipulator inside the TEM to assemble electrochemical cells with ionic liquid or solid state electrolytes, a capability that uses on-chip assembly of battery components on to TEM-compatible multi-electrode arrays, and a capability that uses a TEM-compatible sealed electrochemical cell that we developed for performing in-situ TEM using volatile battery electrolytes. These capabilities were used to understand lithiation mechanisms in nanoscale battery materials, including SnO 2 , Si, Ge, Al, ZnO, and MnO 2 . The modeling approaches used ab initio molecular dynamics to understand early stages of ethylene carbonate reduction on lithiated-graphite and lithium surfaces and constrained density functional theory to understand ethylene carbonate reduction on passivated electrode surfaces. 4 ACKNOWLEDGMENTS

show abstract

Section: Ab Initio MD Of Ec/lithium Interfacessupporting

confidence: 70%

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Leung¹,

Hudak²,

Liu³

et al. 2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…In fact, EC − anion has been observed experimentally. 70 The difference between LUMO/HOMO orbitals of EC − in gas and solution phases was shown in a later study by Yu et al 60 Under the effect of a continuum solvent model, EC can be reduced via one-electron and possibly twoelectron reactions in the solution. By computing the EC reduction pathways with Li + and increasing numbers of EC in Li + (EC) n , Wang et al 15 confirmed the currently generally accepted two-step reduction pathways on the surface that Li + (EC) n is initially reduced to an ion-pair intermediate undergoing homolytic C-O bond cleavage, giving a radical anion coordinated with Li + .…”

Section: Ec Solvent Decomposition Mechanismmentioning

confidence: 89%

“…Following these initial QC calculations, the reduction pathways for EC have been modeled extensively. 15,60,61,[62][63][64][65][66][67][68][69] Typically Li-ion will be surrounded by 4-5 EC in the first solvation shell in the solution. To capture the solvent effect, Wang et al 15 explicitly calculated the possible reduction processes of super-molecules of Li + (EC) n (n = 1-5) using highlevel DFT method in Gaussian 98.…”

Section: Ec Solvent Decomposition Mechanismmentioning

confidence: 99%

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

et al. 2018

View full text Add to dashboard Cite

A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li + transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multiscale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

show abstract

“…[8][9][10][11][12][13] One may argue that its ubiquity and critical role make EC in LIB the battery equivalent of the H 2 O molecule in biology, geochemistry, and many solid-liquid interfacial science disciplines. The present work is indeed modeled after theoretical studies on water-on-mineral surfaces.…”

Section: -3mentioning

confidence: 99%

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces

2012

Self Cite

View full text Add to dashboard Cite

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the initial steps of ethylene carbonate (EC) decomposition on spinel Li 0.6 Mn 2 O 4 (100) surfaces. EC is a key component of the electrolyte used in lithium ion batteries. We predict an slightly exothermic EC bond breaking event on this oxide facet, which facilitates subsequent EC oxidation and proton transfer to the oxide surface. Both the proton and the partially decomposed EC fragment weaken the Mn-O ionic bonding network. Implications for interfacial film made of decomposed electrolyte on cathode surfaces, and Li x Mn 2 O 4 dissolution during power cycling, are discussed. keywords: lithium ion batteries; lithium manganate; ethylene carbonate; density functional theory; ab initio molecule dynamics; computational electrochemistry 1

show abstract

Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate

Cited by 80 publications

References 52 publications

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces

Contact Info

Product

Resources

About

Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate

Cited by 80 publications

References 52 publications

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on LixMn2O4(100) Surfaces

Contact Info

Product

Resources

About

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li_xMn₂O₄(100) Surfaces