title: Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.
abstract: The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.
authors.affiliation: Materials Science Research Laboratory, Central Research Institute of Electric Power Industry , 2-11-1 Iwado Kita, Komae, Tokyo 201-8511, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Kobayashi
authors.forename: Yo
authors.initials: Y
authors.lastname: Kobayashi
authors.forename: Masato
authors.initials: M
authors.lastname: Tabuchi
authors.forename: Kumi
authors.initials: K
authors.lastname: Shono
authors.forename: Yasutaka
authors.initials: Y
authors.lastname: Ohno
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Mita
authors.forename: Hajime
authors.initials: H
authors.lastname: Miyashiro