Abstract

AbstractSolid solution of bismuth(III) fluoride (BiF3) and barium(II) fluoride (BaF2) with a variety of crystal structures was prepared, and their electrochemical performances were evaluated on a fluoride shuttle battery (FSB) system. BiF3‐BaF2 based solid solution (Bi1‐xBaxF3‐x (x=0) with orthorhombic phase, x=0.2 with hexagonal phase, and x=0.4 with cubic phase) were successfully obtained with the mechanical alloy method. The change from Bi1‐xBaxF3‐x (x=0) (orthorhombic) to x=0.2 (hexagonal) improved the initial reversible capacity and the capacity retention during cycling. The change from x=0.2 (hexagonal) to 0.4 (cubic) led to further improvement in capacity retention during cycling; however, the initial reversible capacity decreased due to the substitution of excess amount of barium that did not contribute to the redox reaction. For the BiF3‐based compound, controlling the crystal structure and substitution of inactive element affected the FSB performance.

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