Ammonium Fluoride Mediated Synthesis of Anhydrous Metal Fluoride–Mesoporous Carbon Nanocomposites for High-Performance Lithium Ion Battery Cathodes

Metal fluorides (MF x ) are one of the most attractive cathode candidates for Li ion batteries (LIBs) due to their high conversion potentials with large capacities. However, only a limited number of synthetic methods, generally involving highly toxic or inaccessible reagents, currently exist, which has made it difficult to produce well-designed nanostructures suitable for cathodes; consequently, harnessing their potential cathodic properties has been a challenge. Herein, we report a new bottom-up synthetic method utilizing ammonium fluoride (NH 4 F) for the preparation of anhydrous MF x (CuF 2, FeF 3, and CoF 2 )/mesoporous carbon (MSU–F–C) nanocomposites, whereby a series of metal precursor nanoparticles preconfined in mesoporous carbon were readily converted to anhydrous MF x through simple heat treatment with NH 4 F under solventless conditions. We demonstrate the versatility, lower toxicity, and efficiency of this synthetic method and, using XRD analysis, propose a mechanism for the reaction. All MF x /MSU–F–C prepared in this study exhibited superior electrochemical performances, through conversion reactions, as the cathode for LIBs. In particular, FeF 3 /MSU–F–C maintained a capacity of 650 mAh g –1 FeF3 across 50 cycles, which is ∼90% of its initial capacity. We expect that this facile synthesis method will trigger further research into the development of various nanostructured MF x for use in energy storage and other applications.