Perovskite-type solid electrolytes exhibit a diverse range of conductive properties due to the competition and coupling of multiple degrees of freedom. In perovskite structures, B-site and X-site ions form topological octahedral sublattices, which are instrumental in regulating transport properties for various charge carriers. However, research focused on the relationship between octahedral distortion and conductive properties in perovskite-type proton conductors remains limited. In this study, dopants such as Ge, Sn, Pr, and Ce were selected to modify the degree of BO6 octahedral distortion in CaHf0.9Sc0.1O3-δ . The relationships between conductivity, transport number, mobility, and the distortion degree were systematically investigated. The data indicate that both proton and oxygen ion mobilities initially increase with the octahedral distortion angle and then decrease, and CaHf0.8Sn0.1Sc0.1O3-δ with an octahedral distortion angle of 15.6°, exhibited the highest ionic mobilities and conductivities. The BO6 octahedral distortion appears to limit oxide ion conduction while enhancing the proton transport number. However, excessive doping generates additional oxygen vacancies, which adversely affect proton conduction. Under the combined influence of these factors, CaHf0.8Ce0.1Sc0.1O3-δ achieved the highest proton transport number of 0.503 at 800 °C. Overall, this work provides insights into the relationship between octahedral distortion and conductive properties, suggesting that co-doping is a feasible approach for further regulating carrier mobility properties.
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