A group of ferrocene‐containing polymers were synthesized from vinylferrocene, ethynylferrocene and 1,1′‐dibromoferrocene, and properties of the formed polymers were examined to clarify their potential as a new class of cathode‐active, charge‐storage materials for rechargeable batteries. Vinylferrocene polymerized with 2,2′‐azoisobutyronitrile (AIBN) to give a polymer with number‐average molecular weights of 2 200–5 100 g · mol−1 in 12–41% yields, while ethynylferrocene and 1,1′‐dibromoferrocene polymerized with Rh catalysts and by step‐growth mechanism, respectively, to provide insoluble polymers in 71–96% yields. The capacities of organometallic rechargeable cells fabricated with poly(vinylferrocene), poly(ethynylferrocene), and poly(ferrocene) reached 105, 105, and 95 Ah · kg−1, respectively. In particular, poly(vinylferrocene) displayed completely reversible charge/discharge processes featuring a constant voltage of around 3.5 V.magnified image

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Molecular clusters such as the Mn12 cluster (Mn12) can be used as a cathode-active material in Li batteries. X-ray absorption fine structure studies on the cathode materials in Mn12 molecular cluster batteries demonstrated that the charging/discharging processes include four-electron-redox reaction of Mn12 with a significant change in its molecular structure.

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