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Abstract

Exploring electrochemically driven conversion reactions for the development of novel energy storage materials is an important topic as they can deliver higher energy densities than current Li-ion battery electrodes. Conversion-type fluorides promise particularly high energy densities by involving the light and small fluoride anion, and bond breaking can occur at relatively low Li-activity (i.e., high cell voltage). Cells based on such electrodes may become competitors to other envisaged alternatives such as Li-sulfur or Li-air systems with their many unsolved thermodynamic and kinetic problems. Relevant conversion reactions are typically multiphase redox reactions characterized by nucleation and growth processes along with pronounced interfacial and mass transport phenomena. Hence significant overpotentials and nonequilibrium reaction pathways are involved. In this review, we summarize recent findings in terms of phase evolution phenomena and mechanistic features of (oxy) fluorides at different redox stages during the conversion process, enabled by advanced characterization technologies and simulation methods. It can be concluded that well-designed nanostructured architectures are helpful in mitigating kinetic problems such as the usually pronounced voltage hysteresis. In this context, doping and open-framework strategies are useful. By these tools, simple materials that are unable to allow for substantial Li nonstoichiometry (e.g., by Li-insertable channels) may be turned into electroactive materials.