Structural, Electronic, and Electrochemical Properties of LixCo[Fe(CN)(6)](0.90)2.9H(2)O

Prussian blue analogues with jungle-gym-type structure are promising candidates for cathode materials of the lithium-ion secondary battery (LIB). Here, we investigated the structural, electronic, and electrochemical properties of cobalt hexacyanoferrate, LixCo[Fe(CN)(6)](0.90)2.9H(2)O, against Li concentration (x). The capacity (= 139 mAh/g) of the thin-film electrode was close to the ideal value (= 132 mAh/g) for the two-electron reaction. The discharge curve exhibits three plateaus, i. e., plateaus I, II, and III. The material exhibits a first-order phase transition accompanied by significant volume expansion by 7% at the boundary between plateaus II and III. Ex situ X-ray absorption spectroscopy (XAS) indicates that the discharge processes of plateaus I, II, and III are ascribed to the reduction processes of Fe3+, Co3+, and Fe3+, respectively. The rate (r) and cycle (n) dependence of the electrode performance will be discussed in terms of the reduction processes. (C) 2013 The Japan Society of Applied Physics