Abstract
A combined series of in situ and ex situ UV spectroelectrochemical and X-ray absorption studies have been made on MnO2, chemically-modified by small amounts of Bi(III), and comparatively on other MnO2 materials such as a blank (Bi-free) and γ-MnO2. These procedures are applied in order to follow the oxidation-states of Bi and of Mn during the course of discharge and recharge of MnO2 as a battery cathode material, and the extents of rechargeability that can be achieved with such materials. The presence of Bi appears to provide a preferred “heterogeneous” discharge/recharge pathway involving a soluble Mn(III) intermediate, over the alternative “electron-proton” hopping, solid-state mechanism.
From the XAS results, it is concluded that the presence of Bi although not affecting the O-coordination, does influence the Mn-Mn coordination, influencing the way the “MnO2” coordination octahedra are connected.
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Conway, B.E., Qu, D., McBreen, J. (1994). In Situ and Ex Situ Spectroelectrochemical and X-ray Absorption Studies on Rechargeable, Chemically-Modified and Other MnO2 Materials. In: Melendres, C.A., Tadjeddine, A. (eds) Synchrotron Techniques in Interfacial Electrochemistry. NATO ASI Series, vol 432. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-3200-0_18
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DOI: https://doi.org/10.1007/978-94-017-3200-0_18
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