Non-equilibrium metal oxides via reconversion chemistry in lithium-ion batteries

Binary metal oxides are attractive anode materials for lithium-ion batteries. Despite sustained effort into nanomaterials synthesis and understanding the initial discharge mechanism, the fundamental chemistry underpinning the charge and subsequent cycles-thus the reversible capacity-remains poorly understood. Here, we use in operando X-ray pair distribution function analysis combining with our recently developed analytical approach employing Metropolis Monte Carlo simulations and non-negative matrix factorisation to study the charge reaction thermodynamics of a series of Fe- and Mn-oxides. As opposed to the commonly believed conversion chemistry forming rocksalt FeO and MnO, we reveal the two oxide series topotactically transform into non-native body-centred cubic FeO and zincblende MnO via displacement-like reactions whose kinetics are governed by the mobility differences between displaced species. These renewed mechanistic insights suggest avenues for the future design of metal oxide materials as well as new material synthesis routes using electrochemically-assisted methods. The charging of Fe and Mn oxide anodes in lithium-ion batteries are believed to form rocksalt phases via reconstructive conversion reactions. Here, the authors show that MxOy (M=Fe, Mn) transform into non-native body-centred cubic FeO and zincblende MnO via topotactic displacement-like pathways.

Automated summary

This study reveals the charge reaction thermodynamics of Fe and Mn oxides using in operando X-ray pair distribution function analysis and analytical approach employing Metropolis Monte Carlo simulations. The findings suggest potential avenues for the future design of metal oxide materials and new material synthesis routes using electrochemically-assisted methods.