Computational Design to Suppress Thermal Runaway of Li-Ion Batteries via Atomic Substitutions to Cathode Materials

[Image: see text] The cathode material of a lithium-ion battery is a key component that affects durability, capacity, and safety. Compared to the LiCoO(2) cathode material (the reference standard for these properties), LiNiO(2) can extract more Li at the same voltage and has therefore attracted considerable attention as a material that can be used to obtain higher capacity. As a trade-off, it undergoes pyrolysis relatively easily, leading to ignition and explosion hazards, which is a challenge associated with the application of this compound. Pyrolysis has been identified as a structural phase transformation of the layered rocksalt structure → spinel → cubic rocksalt. Partial substitution of Ni with various elements can reportedly suppress the transformation and, hence, the pyrolysis. It remains unclear which elemental substitutions inhibit pyrolysis and by what mechanism, leading to costly material development that relies on empirical trial and error. In this study, we developed several possible reaction models based on existing reports, estimated the enthalpy change associated with the reaction by ab initio calculations, and identified promising elemental substitutions. The possible models were narrowed down by analyzing the correlations of the predicted dependence of the reaction enthalpies on elemental substitutions, compared between different reaction models. According to this model, substitution by P and Ta affords the highest enthalpy barrier between the initial (layered rocksalt) and the final (cubic rocksalt) structures but promotes the initial transformation to spinel as a degradation. Substitution by W instead generates the barrier to the final (preventing dangerous incidents) process, as well as for the initial degradation to spinel; therefore, it is a promising strategy to suppress the predicted pyrolysis.