Hydrogen Bond Strength Dictates the Rate-Limiting Steps of Diffusion in Proton-Conducting Perovskites:A Critical Length Perspective

Abstract: Proton-conducting solid oxide fuel cells (PC-SOFCs) are pivotal for their high proton conductivity and superior performance. The proton conduction mechanism is commonly described by the Grotthuss mechanism, involving proton rotation and transfer. While proton transfer is often considered the rate-limiting step, the underlying reasons remain unclear. Through density functional theory calculations on undoped, A-site doped, and B-site doped BaHfO$_3$ systems, we demonstrate that the rate-limiting nature of proton transfer stems from the formation of weaker hydrogen bonds. In systems with strong hydrogen bonds, proton rotation becomes non-negligible. We identify a critical hydrogen bond length that distinguishes strong from weak bonds, with shorter lengths correlating with distorted perovskite structures and configurations deviating from cubic. This insight into the necessity of rotation is crucial for screening and optimizing materials with superior proton conduction properties.