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Title: Lithium Ethylene Dicarbonate Identified as the Primary Product ofChemical and Electrochemical Reduction of EC in EC:EMC/1.2M LiPF6Electrolyte

Abstract

Lithium ethylene dicarbonate (CH2OCO2Li)2 was chemically synthesized and its Fourier Transform Infrared (FTIR) spectrum was obtained and compared with that of surface films formed on Ni after cyclic voltammetry (CV) in 1.2M lithium hexafluorophosphate(LiPF6)/ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7, w/w) electrolyte and on metallic lithium cleaved in-situ in the same electrolyte. By comparison of IR experimental spectra with that of the synthesized compound, we established that the title compound is the predominant surface species in both instances. Detailed analysis of the IR spectrum utilizing quantum chemical (Hartree-Fock) calculations indicates that intermolecular association through O...Li...O interactions is very important in this compound. It is likely that the title compound in passivation layer has a highly associated structure, but the exact intermolecular conformation could not be established based on analysis of the IR spectrum.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Sponsoring Org.:
USDOE. Assistant Secretary for Energy Efficiency andRenewable Energy. Office of the FreedomCAR and Vehicle TechnologyProgram
OSTI Identifier:
860350
Report Number(s):
LBNL-57579
R&D Project: 673501; BnR: VT0301030; TRN: US200524%%105
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry B; Journal Volume: 109; Journal Issue: 37; Related Information: Journal Publication Date: 2005
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; CARBONATES; ELECTROLYTES; ETHYLENE; LITHIUM; PASSIVATION; SPECTRA

Citation Formats

Zhuang, Guorong V., Xu, Kang, Yang, Hui, Jow, T. Richard, and RossJr., Philip N. Lithium Ethylene Dicarbonate Identified as the Primary Product ofChemical and Electrochemical Reduction of EC in EC:EMC/1.2M LiPF6Electrolyte. United States: N. p., 2005. Web. doi:10.1021/jp052474w.
Zhuang, Guorong V., Xu, Kang, Yang, Hui, Jow, T. Richard, & RossJr., Philip N. Lithium Ethylene Dicarbonate Identified as the Primary Product ofChemical and Electrochemical Reduction of EC in EC:EMC/1.2M LiPF6Electrolyte. United States. doi:10.1021/jp052474w.
Zhuang, Guorong V., Xu, Kang, Yang, Hui, Jow, T. Richard, and RossJr., Philip N. Wed . "Lithium Ethylene Dicarbonate Identified as the Primary Product ofChemical and Electrochemical Reduction of EC in EC:EMC/1.2M LiPF6Electrolyte". United States. doi:10.1021/jp052474w. https://www.osti.gov/servlets/purl/860350.
@article{osti_860350,
title = {Lithium Ethylene Dicarbonate Identified as the Primary Product ofChemical and Electrochemical Reduction of EC in EC:EMC/1.2M LiPF6Electrolyte},
author = {Zhuang, Guorong V. and Xu, Kang and Yang, Hui and Jow, T. Richard and RossJr., Philip N.},
abstractNote = {Lithium ethylene dicarbonate (CH2OCO2Li)2 was chemically synthesized and its Fourier Transform Infrared (FTIR) spectrum was obtained and compared with that of surface films formed on Ni after cyclic voltammetry (CV) in 1.2M lithium hexafluorophosphate(LiPF6)/ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7, w/w) electrolyte and on metallic lithium cleaved in-situ in the same electrolyte. By comparison of IR experimental spectra with that of the synthesized compound, we established that the title compound is the predominant surface species in both instances. Detailed analysis of the IR spectrum utilizing quantum chemical (Hartree-Fock) calculations indicates that intermolecular association through O...Li...O interactions is very important in this compound. It is likely that the title compound in passivation layer has a highly associated structure, but the exact intermolecular conformation could not be established based on analysis of the IR spectrum.},
doi = {10.1021/jp052474w},
journal = {Journal of Physical Chemistry B},
number = 37,
volume = 109,
place = {United States},
year = {Wed May 11 00:00:00 EDT 2005},
month = {Wed May 11 00:00:00 EDT 2005}
}
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  • We present results testing the hypothesis that there is a different reaction pathway for the electrochemical reduction of PC versus EC-based electrolytes at graphite electrodes with LiPF6 as the salt in common. We examined the reduction products formed using ex-situ Fourier Transform Infrared (FTIR) spectroscopy in attenuated total reflection (ATR) geometry. The results show the pathway for reduction of PC leads nearly entirely to lithium carbonate as the solid product (and presumably ethylene gas as the co-product) while EC follows a path producing a mixture of organic and inorganic compounds. Possible explanations for the difference in reaction pathway are discussed.
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