The Li/Li+ Reference Electrode in Propylene Carbonate

Burrows, Brian; Jasinski, Raymond

doi:10.1149/1.2411199

Cited by 48 publications

(29 citation statements)

References 3 publications

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“…A single-compartment cell with three electrodes was used for cyclic voltammetry (CV) experiments. Lithium metal was used for both counter and reference electrodes [8]. A rigorously polished glassy carbon disk electrode (GC, ∅=0.7 mm) was employed as the working electrode in CV.…”

Section: Methodsmentioning

confidence: 99%

In-situ FTIR investigations on the reduction of vinylene electrolyte additives suitable for use in lithium-ion batteries

Santner

Korepp

Winter

et al. 2004

Analytical and Bioanalytical Chemistry

101

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Lithium-ion batteries operate beyond the thermodynamic stability of the aprotic organic electrolyte used and electrolyte decomposition occurs at both electrodes. The electrolyte must therefore be composed in a way that its decomposition products form a film on the electrodes which stops the decomposition reactions but is still permeable to the Li(+) cations which are the charge carriers. At the graphite anode, this film is commonly referred to as a solid electrolyte interphase (SEI). Aprotic organic compounds containing vinylene groups can form an effective SEI on a graphitic anode. As examples, vinyl acetate (VA) and acrylonitrile (AN) have been investigated by in-situ Fourier transform infrared (FTIR) spectroscopy in a specially developed IR cell. The measurements focus on electrolyte decomposition and the mechanism of SEI formation in the presence of VA and AN. We conclude that cathodic reduction of the vinylene groups (i.e., via reduction of the double bond) in the electrolyte additives is the initiating and thus a most important step of the SEI-formation process, even in an electrolyte which contains only a few percent (i.e. electrolyte additive amounts) of the compound. The possibility of electropolymerization of the vinylene monomers in the battery electrolytes used is critically discussed on the basis of the IR data obtained.

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Section: Methodsmentioning

confidence: 99%

In-situ FTIR investigations on the reduction of vinylene electrolyte additives suitable for use in lithium-ion batteries

Santner

Korepp

Winter

et al. 2004

Analytical and Bioanalytical Chemistry

101

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show abstract

“…At short time, there is a shift of the potential of metallic lithium with the time due to the formation of the SEI layer and solvated electrons [11]. Thereafter, if the lithium is properly cleaned, the potential of the metallic lithium is stable for several days [12].…”

Section: Introductionmentioning

confidence: 99%

Reliable reference electrodes for lithium-ion batteries

Mantia

Wessells

Deshazer

et al. 2013

Electrochemistry Communications

120

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“…1 may be accounted for by a small change in the value of the junction potential, Ej, of Eq. [1]. The H20 concentration of the reference electrode compartment is maintained at a very low level.…”

Section: Rt (A+)mentioning

confidence: 99%

“…In this paper we describe electrochemical studies of uranium(IV) and thorium(IV) in a basic fluoride solvent L~F-NaF-KF [46.5-11.5-42.0 m/o (mole per cent) ] at 500~ Electrochemical studies of uranium in other molten fluorides have been described (1)(2)(3)(4) and the results of these investigations have been summarized by one of us (5). The U(IV) reduction in the more acidic LiF-BeF~-ZrF4 (65.6-29.4-5.0 m/o) at 500~ was shown (1, 2) to be a reversible, one-electron process occurring at -,, --1.5V (vs. the unit mole fraction Ni(II)/Ni couple).…”

Section: Rt (A+)mentioning

confidence: 99%

On the Transference Number for Li[sup +] Ion in Propylene Carbonate Solutions from EMF Measurements

Hoare¹,

Wiese²

1974

J. Electrochem. Soc.

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The rest potential of a Li/Li + electrode was determined with respect to a Li/Li +, 1M reference electrode in propylene carbonate solutions of LiC104 as a function of the Li + ion concentration and of the H20 concentration. The transference number for Li + ion was determined from these data and found to be 0.32. This value is virtually independent of the amount of H20 present in the PC solution. For low water content, the electrode is one of the first kind and the potential is determined by the Li/Li + reaction. At high water content, the electrode becomes one of the second kind and the potential is determined by the Li/LiOH reaction. The transition from one reaction to the other takes place where, on the average, one H20 molecule replaces one PC molecule in the solvation sheath of each Li + ion.To investigate the electrochemical properties of the light, highly reactive metal electrode systems, it is desirable to use an aprotic nonaqueous electrolyte. In the search for a suitable reference electrode for the study of such a system, the possibility of employing the Li/Li § couple in propylene carbonate (PC) was considered since this couple has been reported (1) to be reversible and well behaved. From chronopotentiometric and cyclic voltammetric studies (2,3), it appears that the presence of water in this system may play (3) a complex role. Keller and associates (4) report that the mobility of the Li + ion in PC is very low (t+ ~ 0.25) as determined from conductance measurements. Solvation of the Li + ion may account for the low value of the transference number, t+.Using a reference electrode composed of a Li rod in 1M LiC104 in PC, the potential of a concentration cell, Li/LiC104 (C = x), PC 3 PC, LiC104 (1M)/Li, was investigated as a function ~)f the Li + ion and H20 concentration. Some information about the effect of H20 on the ionic mobilities and on the potential-determining reactions at the Li electrode can be obtained from these studies. This report describes the results of such an investigation since to these authors' knowledge this information is not available in the reviewed literature. ExperimentalAll experiments were carried out in a glove box in an argon atmosphere in which the oxygen, nitrogen, and water content are maintained below 1 ppm. The PC was vacuum (2 Torr) distilled in a still with a Podbilniak column and the first 30% of the still pot charge was discarded. The next 60% of the pot charge was used in the experiments. Ultrapure LiC104 certified to contain less than 20 ppm H20 was used to make up a stock solution of 1M LiC104 in PC. Further traces of H20 were removed from these solutions by gettering with scraped Li foil until no water was detected by a Karl Fischer titration (<5 ppm H~O). Such treated solutions will be referred to as dry solutions.After investigating a number of designs for the envelope of our reference electrode including cracked glass, wetted ground glass, and asbestos fiber junctions, the best performance was obtained with glass frits. A glass tube (13.5 cm long sealed at on...

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The Li/Li+ Reference Electrode in Propylene Carbonate

Abstract: not Available.

Cited by 48 publications

References 3 publications

In-situ FTIR investigations on the reduction of vinylene electrolyte additives suitable for use in lithium-ion batteries

In-situ FTIR investigations on the reduction of vinylene electrolyte additives suitable for use in lithium-ion batteries

Reliable reference electrodes for lithium-ion batteries

On the Transference Number for Li[sup +] Ion in Propylene Carbonate Solutions from EMF Measurements

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