Analysis and distillation of propylene carbonate

Jasinski, Raymond; Kirkland, S.

doi:10.1021/ac50156a051

Cited by 85 publications

(38 citation statements)

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“…Its wide liquid range (defined by the difference between T m and T b , Table 1), high dielectric constant, and inert stability with lithium made it a favored solvent. Considerable efforts were also made to purify it [4] when a less than ideal plating efficiency (≤85%) for lithium was observed during cycling. The first generation of the commercial lithium ion cells adopted by Sony that belong to a PC-based electrolyte was used, and later, it was replaced by another member of the family, i.e., high melting ethylene carbonate (EC).…”

Section: Choice Of Solventsmentioning

confidence: 99%

“…The reactivity of LiBF 4 with lithium was suspected as discoloration occurred with time or heating [68]. More recent studies on its ionics and limiting properties in various nonaqueous systems established that, among the most common anions encountered, BF 4 − has the highest mobility, but its dissociation constant is considerably smaller than those of LiAsF 6 and LiPF 6 [42,69]. The unfavorable balance of these two properties results in the moderate ion conductivity.…”

Section: Choice Of the Lithium Saltsmentioning

confidence: 99%

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RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

Ahmad

2009

Ionics

111

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Polymer electrolytes are an important component of many electrochemical devices. This paper reviews stateof-the-art of the electrochemical and physical properties of polymer electrolytes. This review mainly encompasses the properties of different salts, solvents, and polymer hosts, which are encaged in liquid electrolytes. The additions of filler in polymer electrolytes result in composite polymer electrolytes, having high mechanical integrity and ionic conductivity, that are ideal electrolyte for these applications. The next generation state-of-the-art room-temperature ionic liquids based electrolytes, which are far superior to corresponding nonionic solvent-based electrolytes, are also discussed.

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Section: Choice Of Solventsmentioning

confidence: 99%

Section: Choice Of the Lithium Saltsmentioning

confidence: 99%

RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

Ahmad

2009

Ionics

111

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“…After this time, approximately 450 ml of solution was transferred from the storage vessel to the deoxygenation flask. V U H P N2 was passed through the solution at a rate of about 100 ml/min for at least 40 h. This is an adaptation of a technique shown by Jasinski and Kirkland (13) to reduce the water content to less than 0.5 ppm for LiC104 solutions. Earlier work by Kelly et al (3) on LiC104 solutions revealed that this purification procedure produced PC/LiC104 solutions containing less than 5 ppm H20.…”

Section: Methodsmentioning

confidence: 99%

The Passivity of 304 Stainless Steel in Propylene Carbonate Solutions

Shifler

Moran

Krüger

1992

J. Electrochem. Soc.

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The passivation behavior of 304 stainless steel in anhydrous propylene carbonate (PC) containing 0.5M LiAsF6 or 0.5M LiC104 was studied. The air-formed film on 304SS is stable up to the oxidation potential of PC (PCox). Scratch tests show that the bared 304SS surface repassivates in the anhydrous PC solutions of either electrolyte by chemisorption of PC molecules below PCox. In PC/0.5M LiAsF6 solutions, the 304SS is not passivated at potentials above PCox. In PC/0.5M LiC104 solutions the 304SS is passive at potentials 400-500 mV above PCox. This is attributed to the formation of a thin metastable perchlorate salt film or an adsorbed layer of perchlorate anions. When the perchlorate anions oxidize, the passivation becomes unstable and pitting occurs. Small (3-8 volume percent) additions of PC/0.5M LiC104 to PC/0.5M LiAsF6 solutions raises the passive range to the perch]orate oxidation potential. Small quantities of water, propylene glycol, and propylene oxide added to PC slightly improve the passive range of the 304 stainless steel.The increasing importance of lithium battery technology in a wide variety of applications has demonstrated a need for more reliable, longer-lived cells. Because of the reactivity of lithium in protic solvents such as water, aprotic organic solvents are used in most lithium batteries. Such solvents include propylene carbonate (PC), 1,2-dimethoxyethane (DME), 2-methyltetrahydrofuran (2-MeTHF), and more recently, mixtures of PC/2MeTHF and PC/DME (1). A wide variety of electrolytes have been used, but the most common are LiC104, LiA1C14, LiPF6, and more recently, LiAsF6 (2). The corrosive nature of these solutions is apparent based upon the fact that various types of stainless steels must often be used to encase such batteries. Passivity in aqueous solutions has been studied extensively. Comparatively little work has been done on the nature of the passive film and the breakdown of passivity on metals in nonaqueous solvents. The nature of the passive film on metal or alloy surfaces usually determines its protective and/or its corrosive behavior in aqueous environments and should establish its protective and corrosive nature in nonaqueous solvents.The purpose of this study was to investigate the passivity and the breakdown of passivity of 304 stainless steel in neutral anhydrous propylene carbonate (PC) containing either 0.5M LiAsF6 or 0.5M LiC104 electrolyte, and to determine the influence of common PC impurities. The influence of small additions of PC/LiC104 to PC/LiAsF6 solutions was also investigated and produced some surprising results. Previous work has studied the passive behavior of 99.995% iron in PC solutions (3-6) and 99.995% iron in PC-H20 mixtures (4, 7). Other examinations have investigated the passive behavior of 1018 carbon steel in PC solutions (5, 6) and mixed PC-H20 solutions (6), and nickel 200 in PC and mixed PC-H20 solvents (6).The mechanisms by which a metal can passivate can be classified into four types: (i) air-formed film, (ii) salt film formation, (iii) chemisorpti...

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“…If our search for reactive impurities in PC and GBL appears to have a certain Edisonian component, it is because important contaminants have escaped identification in the past in spite of thorough gas chromatographic studies in PC [ 16,26,27]. We advocate the experimental protocol described here for the reasons indicated in the Introduction section and because it proved highly effective in detecting and determining previously unsuspected impurities, particularly amines, in reagent grade alcohols [1,17].…”

Section: Results and Mscusionmentioning

confidence: 99%

“…Careful gas chromatographic studies carried out before [16,26] have shown that PC, even after purification by any of a number of procedures, may still contain a plethora of impurities, viz., water, carbon dioxide, ethylene carbonate, 1,2-propylene oxide, ally1 alcohol, and 1,2-and 1,3-propanediol. Fortunately, the concentrations of the majority of these impurities could be lowered to below lo-' or even M by careful fractionation, but even such low concentrations can be harmful in certain uses of the solvent, as described elsewhere [1,17].…”

Section: Gas Chromatography Of Propylene Carbonatementioning

confidence: 99%

Studies on the response of potentiometric sensors and the characterization of reactive impurities in propylene carbonate and gamma‐butyrolactone as solvents

et al. 1993

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This article deals with an experimental protocol developed to characterize reactive impurities that seriously compromise the utility of relatively inert solvents such as those discussed here. It was found that potentiometric sensors for hydrogen, silver(I), and copper(I1) ions give Nernstian response over a broad activity range in solutions of widely differing buffer capacity in y-butyrolactone (GBL), a promising but inadequately explored solvent for a variety of applications. Advantage was taken of the proper response of these sensors in applying the "ion probe method" described before to characterize impurities in both unpurified and purified y-butyrolactone on the basis of their reactivities rather than their concentrations alone. The same sensors were also used in conventional potentiometric titrations of impurities in propylene carbonate (PC), a solvent that has been extensively used in fundamental studies of solute-solvent interactions as well as in the construction of commercial lithium batteries. The results of the potentiometric studies served as a guide in the design of appropriate gas chromatographic measurements. Three impurities not reported before were found in a reagent grade propylene carbonate: triethylamine and chloride ion, both at concentrations above M, as well as 1,2-dibromopropane. The effectiveness of different purification procedures was studied.

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Analysis and distillation of propylene carbonate

Cited by 85 publications

References 1 publication

RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

The Passivity of 304 Stainless Steel in Propylene Carbonate Solutions

Studies on the response of potentiometric sensors and the characterization of reactive impurities in propylene carbonate and gamma‐butyrolactone as solvents

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