title: In situ observation of macroscopic phase separation in cobalt hexacyanoferrate film.
abstract: Lithium-ion secondary batteries (LIBs) store electric energy via Li+deintercalation from cathode materials. The Li+deintercalation frequently drives a first-order phase transition of the cathode material as a result of the Li-ordering or Li-concentration effect and causes a phase separation (PS) into the Li-rich and Li-poor phases. Here, we performed an in situ microscopic investigation of the PS dynamics in thin films of cobalt hexacyanoferrate, LixCo[Fe(CN)6]0.9, against Li+deintercalation. The thick film (d = 1.5 μm) shows a characteristic macroscopic PS of several tens of μm into the green (Li1.6Co[Fe(CN)6]0.9) and black (Li.6Co[Fe(CN)6]0.9) phases in the x range of 1.0 < x < 1.6. Reflecting the substrate strain, the thin film (d = 0.5 μm) shows no trace of the PS in the entire x region. Our observation suggests that the macroscopic PS plays a significant role in the charge/discharge dynamics of the cathode.
authors.affiliation: Graduate School of Pure and Applied Science, University of Tsukuba, Tsukuba 305-8571, Japan.
authors.forename: Masamitsu
authors.initials: M
authors.lastname: Takachi
authors.affiliation: Graduate School of Pure and Applied Science, University of Tsukuba, Tsukuba 305-8571, Japan.|Center for Integrated Research in Fundamental Science and Engineering (CiRfSE), University Tsukuba, Tsukuba 305-8571, Japan.|Tsukuba Research Center for Interdisciplinary Materials Sciences (TIMS), University of Tsukuba, Tsukuba 305-8571, Japan.|Faculty of Pure and Applied Science, University of Tsukuba, Tsukuba 305-8571, Japan.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Moritomo