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Raman spectral and electrochemical studies of lithium/electrolyte interfaces

Abstract

Cyclic voltammetry, corrosion potential-time transients and Normal Raman spectroscopy have been employed to characterize the lithium-lithium salt, organic solvent, interfacial region. An in-situ cutting technique was developed to expose lithium metal. In-situ optical and ex-situ scanning electron microscopy (SEM) have been used to examine the morphology of the lithium electrode surface during exposure at open circuit and after anodic polarization. The main reaction product detected by in-situ Raman spectroscopy in the system/lithium/LiAsF[sub 6], tetrahydrofuran (THF) electrolyte was polytetrahydrofuran (PTHF). The conditions for the polymerization reaction in the presence of lithium metal have been determined. Tetrahydrofuran (THF) decomposition reaction mechanisms are discussed. Decomposition reaction products have been determined as arsenic (II) oxide, As[sub 2]O[sub 3] (arsenolite) and arsenious oxyfluoride AsF[sub 2]-O-AsF[sub 2]. Potentiodynamic polarization measurements revealed a substantial shift of the corrosion potential towards positive values and only a moderate increase of anodic dissolution current for in-situ cut lithium metal. Corrosion potential-time merits have been measured. The following electrolytes have been investigated: LiAsF[sub 6], LiPF[sub 6], LiClO[sub 4], and Li(CF[sub 3]SO[sub 2])[sub 2]N in THF, 2Me-THF, and propylene carbonate (PC). The transients permit the ranking of the reactivity of the electrolytes. These measurements have shed light on understanding the stability of  More>>
Authors:
Publication Date:
Jan 01, 1922
Product Type:
Miscellaneous
Reference Number:
EDB-94-082485
Resource Relation:
Other Information: Thesis (Ph.D.). Order No. DANN-75,790
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTROLYTES; INTERFACES; RAMAN SPECTRA; VOLTAMETRY; LITHIUM; ELECTROCHEMICAL CORROSION; ELECTROCHEMISTRY; ALKALI METALS; CHEMICAL REACTIONS; CHEMISTRY; CORROSION; ELEMENTS; METALS; SPECTRA; 400400* - Electrochemistry
OSTI ID:
7273823
Research Organizations:
Waterloo Univ., ON (Canada)
Country of Origin:
Canada
Language:
English
Other Identifying Numbers:
Other: ISBN: 0-315-75790-6
Availability:
Micromedia Ltd., 144 Front St. West, Toronto Ontario N5J 2L (Canada)
Submitting Site:
IIA
Size:
Pages: (322 p)
Announcement Date:
May 13, 2001

Citation Formats

Odziemkowski, M. Raman spectral and electrochemical studies of lithium/electrolyte interfaces. Canada: N. p., 1922. Web.
Odziemkowski, M. Raman spectral and electrochemical studies of lithium/electrolyte interfaces. Canada.
Odziemkowski, M. 1922. "Raman spectral and electrochemical studies of lithium/electrolyte interfaces." Canada.
@misc{etde_7273823,
title = {Raman spectral and electrochemical studies of lithium/electrolyte interfaces}
author = {Odziemkowski, M}
abstractNote = {Cyclic voltammetry, corrosion potential-time transients and Normal Raman spectroscopy have been employed to characterize the lithium-lithium salt, organic solvent, interfacial region. An in-situ cutting technique was developed to expose lithium metal. In-situ optical and ex-situ scanning electron microscopy (SEM) have been used to examine the morphology of the lithium electrode surface during exposure at open circuit and after anodic polarization. The main reaction product detected by in-situ Raman spectroscopy in the system/lithium/LiAsF[sub 6], tetrahydrofuran (THF) electrolyte was polytetrahydrofuran (PTHF). The conditions for the polymerization reaction in the presence of lithium metal have been determined. Tetrahydrofuran (THF) decomposition reaction mechanisms are discussed. Decomposition reaction products have been determined as arsenic (II) oxide, As[sub 2]O[sub 3] (arsenolite) and arsenious oxyfluoride AsF[sub 2]-O-AsF[sub 2]. Potentiodynamic polarization measurements revealed a substantial shift of the corrosion potential towards positive values and only a moderate increase of anodic dissolution current for in-situ cut lithium metal. Corrosion potential-time merits have been measured. The following electrolytes have been investigated: LiAsF[sub 6], LiPF[sub 6], LiClO[sub 4], and Li(CF[sub 3]SO[sub 2])[sub 2]N in THF, 2Me-THF, and propylene carbonate (PC). The transients permit the ranking of the reactivity of the electrolytes. These measurements have shed light on understanding the stability of various stability and and solvents in contact with lithium. Compared to purified electrolytes, small amounts of water shift the corrosion potential towards even more positive values. Intensive anodic cycling of a Li electrode in unpurified LiAsF[sub 6]/THF electrolyte leads to the breakdown of a surface film/films. While at the open circuit potential (OCP), water in this same electrolyte leads to crack formation in the bulk lithium electrode.}
place = {Canada}
year = {1922}
month = {Jan}
}