Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries:  Reduction Mechanisms of Ethylene Carbonate

Abstract

Reductive decomposition mechanisms for ethylene carbonate (EC) molecule in electrolyte solutions for lithium-ion batteries are comprehensively investigated using density functional theory. In gas phase the reduction of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron reduction processes. The presence of Li cation considerably stabilizes the EC reduction intermediates. The adiabatic electron affinities of the supermolecule Li(+)(EC)n (n = 1-4) successively decrease with the number of EC molecules, independently of EC or Li(+) being reduced. Regarding the reductive decomposition mechanism, Li(+)(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approximately 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li(+). Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene dicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compound containing an ester group, LiO(CH2)2CO2(CH2)2OCO2Li, then two very competitive reactions of the further reduction of the radical anion and the formation of lithium ethylene dicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compound (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concentration dependence as has also been revealed for the reactions of LiCO3(-) with Li(+)(EC)n; that is, the formation of Li2CO3 is slightly more favorable at low EC concentrations, whereas (CH2OCO2Li)2 is favored at high EC concentrations. On the basis of the results presented here, in line with some experimental findings, we find that a two-electron reduction process indeed takes place by a stepwise path. Regarding the composition of the surface films resulting from solvent reduction, for which experiments usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2OCO2Li, Li(CH2)2OCO2Li and Li2CO3.

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

“…[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.…”

Electrolytes and Interphasial Chemistry in Li Ion Devices

“…It is important to point out that the reduction of neat solvents at electrode surface should be very unlikely due to the rather high activation energy barrier; however, the presence of Li + in the solution and the subsequent formation of its solvation sheath drastically catalyzed such reductions by lowing the energy barrier ( Figure 5) [19].…”

Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes

“…1c) The disparity between gas and solution phase rates likely arises from the repulsive electron affinity of gas phase EC. 12 While electronic structure calculations can impose a metastable isolated "EC − ," the excess e − lies outside the molecule (Fig. 1b); the C E -O 1 anti-bonding orbital is not occupied and bond-breaking is not facilitated.…”