Effect of ligand variation on Mg alkoxyborate electrolytes: Does more fluorine help?

Mg fluorinated alkoxyborate-based electrolytes are promising candidates for rechargeable Mg batteries. In this work, we investigate a series of Mg alkoxyborates with a different degree of anion fluorination in terms of their physicochemical properties, Mg metal anode, and organic cathode electrochemical performance, as well as Mg metal/electrolyte interphase. The results underscore the significant influence of the anion fluorination degree on the transport properties of electrolytes. Notably, the anion with the lowest degree of fluorination exhibits one order of magnitude lower ionic conductivity than electrolytes with more fluorinated anions. Interestingly, the same electrolyte demonstrates the second-best electrochemical performance, with the Mg plating/stripping efficiency close to 99 %. XPS analysis of the Mg metal deposit surface reveals that the high Coulombic efficiency is associated with a high amount of boron-containing species in the metal/electrolyte interphase of the best-performing electrolytes. Additionally, it has been noted that inorganic boron species result in a larger interfacial resistivity for Mg plating/stripping compared to boron species in an organic environment. Testing in combination with organic cathodes reveals the superior performance of the most fluorinated electrolyte in terms of cycling stability and Coulombic efficiency. The present work underlines the interplay of different phenomena affecting the overall electrochemical performance of electrolytes and strategies for the design of next-generation Mg electrolytes.