Ab initio Study of Substitutional Defects in Li_3OCl Solid Electrolyte for Li-ion Batteries

Improving ion transport in solid electrolytes and cathode coatings remains a key challenge for all-solid-state Li-ion batteries because their room-temperature ionic conductivity is still substantially lower than that of liquid electrolytes. In our previous combined experimental and theoretical study, we showed that thermal neutron irradiation enables defect engineering in LiBO2 through the transmutation of 6Li and 10B, generating lattice vacancies that enhance ionic conductivity. Here, we examine whether this approach can be extended to Li3OCl, a representative anti-perovskite solid electrolyte. Using density functional theory, we investigate substitutional defects at Li sites involving B, He, and H, associated with B doping and the neutron-capture reactions 6Li + n → 3H + α and 10B + n → 7Li + α + γ. We evaluate defect formation energetics, the resulting structural distortions, and compare these substitutional defects with other mono-, di-, and tri-cation substitutions at Li sites. Our results show that substitutional defects associated with neutron irradiation provide a feasible route to tune the defect chemistry of antiperovskite solid electrolytes and support neutron-driven defect engineering as a strategy for developing advanced materials for high-performance all-solid-state Li-ion batteries.