A phenomenological expression of solid‐state redox potentials is proposed in order to understand anomalous voltage behaviors of the insertion materials and . The method consists of the superposition of each redox system characterized by Eq. 4 and 5 (see text), describing both one‐phase and two‐phase reactions by adjusting the interaction‐energy parameter z ϕ i . For the reaction of , the reversible electrode potentials, E ( y ), which are observable, are obtained in a self‐consistent manner from the electrochemical density of states. A thus‐described solid‐state electrochemical reaction consists of three redox systems characterized by E 0i = 4.50, 4.18 and 391 V for ; 4.23, 3.93, and 3.63 V for ; and 4.58, 4.05, and 3.58 V for . From these results the characteristic features of solid‐state redox electrodes are described and the significance of this method in materials research for advanced batteries is discussed.
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Ohzuku et al. (1997) studied this question.