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Oxidation Potential and Absolute Hardness Relationship in Lithium-ion Battery Electrolytes

Article of Honda R&D Technical Review Vol.33 No.1


In this paper, we investigated the increase in oxidative stability of electrolytes in order to respond to the high-voltage operation of Li-ion rechargeable batteries. DFT geometry optimization calculations were performed for those molecular models of which side chain in the carbonate solvent substituted with a fluorinated alkyl group and the carbon in the main chain substituted with sulfur or oxygen. Linear correlation was found between the absolute hardness calculated from the frontier orbital energy following structural optimization and the oxidation potential determined by linear sweep voltammetry. Taking absolute hardness as an index, a mixed solvent of fluorinated alkyl ether and sulfolane, which was predicted to have better oxidative stability than carbonate solvent, was prepared as a prototype electrolyte. We then measured discharge capacity retention by a cyclic charge-discharge test using a battery with LiNi0.5Mn1.5O4, which is a well-known cathode material for high-potential operation. The result showed that the number of cycles taken to reach a discharge capacity retention index of 80% increased from 45 cycles, which is the figure when using carbonate electrolyte, to 80 cycles, which is the prototype.


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Author (organization or company)

Yoshiyuki MORITA(Innovative Research Excellence)、Hiroto MAEYAMA(Innovative Research Excellence)、Atsushi FURUKAWA(Innovative Research Excellence)

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