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Reconsidering Anode Materials for Fluoride-Ion Batteries - The Unexpected Roles of Carbide Formation.

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Carbon is a ubiquitous additive to enhance the electrical conductivity of battery electrodes. Although carbon is generally assumed to be inert, the poor reversibility seen in some fluoride-ion battery electrodes… Click to show full abstract

Carbon is a ubiquitous additive to enhance the electrical conductivity of battery electrodes. Although carbon is generally assumed to be inert, the poor reversibility seen in some fluoride-ion battery electrodes has not been explained or systematically explored. Here, we utilize the Materials Project database to assess electrode deactivation reactions that result in the formation of a metal carbide. Specifically, we compare the theoretical potentials of MFy reduction to either the corresponding metal or metal carbide MCx. We find that the formation of MCx is unlikely to be important in anodes that operate at modest reduction potentials, such as those made from electronegative metals like Zn, Sn, or Pb.  However, in anodes that operate at extreme reduction potentials, such as alkaline earths or lanthanides, we find that formation of MCx is relevant and can emerge as a mechanism for capacity loss. Thus, side reactions of metals with carbon additives that form metal carbides offer a possible explanation of the poor reversibility of lanthanide- or alkaline earth metal-based electrode materials. Finally, we highlight that the carbide formation process might be exploited for designing cheap anode systems with improved reversibility.

Keywords: fluoride ion; carbide formation; reconsidering anode; formation; metal

Journal Title: ChemSusChem
Year Published: 2023

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