Solid-State Chemistries Stable with High-Energy Cathodes for Lithium-Ion Batteries

In the pursuit of higher-energy-density lithium-ion batteries, one major challenge is the stability of high-capacity or high-voltage cathodes with electrolytes. An understanding of how different chemistries interact with high-energy cathodes is required to enable the rational design of coatings or solid electrolyte materials that offer long-term stability with the cathode. Here, we systematically evaluated the thermodynamic stability among a broad range of solid-state chemistries with common cathodes. Our thermodynamic analyses confirmed that the strong reactivity of lithiated and delithiated cathodes greatly limits the possible choice of materials that are stable with the cathode under voltage cycling. Our computation reaffirmed previously demonstrated coating and solid electrolyte chemistries and suggested several new stable chemistries. In particular, the lithium phosphates and lithium ternary fluorides, which have high oxidation limits, are promising solid-state chemistries stable with high-voltage cathodes. Our study provides guiding principles for selecting materials with long-term stability with high-energy cathodes for next-generation lithium-ion batteries.