Oxide Cathodes: Functions, Instabilities, Self Healing, and Degradation Mitigations

Recent progress in high-energy-density oxide cathodes for lithium-ion batteries has pushed the limits of lithium usage and accessible redox couples. It often invokes hybrid anion- and cation-redox (HACR), with exotic valence states such as oxidized oxygen ions under high voltages. Electrochemical cycling under such extreme conditions over an extended period can trigger various forms of chemical, electrochemical, mechanical, and microstructural degradations, which shorten the battery life and cause safety issues. Mitigation strategies require an in-depth understanding of the underlying mechanisms. Here we offer a systematic overview of the functions, instabilities, and peculiar materials behaviors of the oxide cathodes. We note unusual anion and cation mobilities caused by high-voltage charging and exotic valences. It explains the extensive lattice reconstructions at room temperature in both good (plasticity and self-healing) and bad (phase change, corrosion, and damage) senses, with intriguing electrochemomechanical coupling. The insights are critical to the understanding of the unusual self-healing phenomena in ceramics (e.g., grain boundary sliding and lattice microcrack healing) and to novel cathode designs and degradation mitigations (e.g., suppressing stress-corrosion cracking and constructing reactively wetted cathode coating). Such mixed ionic-electronic conducting, electrochemically active oxides can be thought of as almost "metalized" if at voltages far from the open-circuit voltage, thus differing significantly from the highly insulating ionic materials in electronic transport and mechanical behaviors. These characteristics should be better understood and exploited for high-performance energy storage, electrocatalysis, and other emerging applications.