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

Identifying the rate-limiting step of proton migration in proton-conducting oxides is essential for assessing and regulating proton conductivity. Proton migration based on the Grotthuss mechanism involves both proton rotation and proton transfer, with the latter typically regarded as the rate-limiting step. However, a universal criterion for identifying the rate-limiting step remains to be established. Here, we perform a quantitative decomposition of the rotation and transfer barriers, revealing that the hydrogen bond to the acceptor oxygen dictates their energy barrier difference via the O i –B–O f bending mechanism. Based on the energy difference associated with a one-order-of-magnitude variation in residence time, we propose the hydrogen bond length criterion for identifying the rate-limiting step across operating temperatures. Taking the 500 K criterion as an upper limit, when the hydrogen bond length of systems falls below 2.05 Å, proton rotation becomes competitive with transfer. Applied to a wider range of perovskite materials, this criterion predicts comparable rotation and transfer rates in cubic structures with small lattice constants, low-valent B-site doped systems with moderate ionic radii, and distorted orthorhombic structures. Our findings provide an atomic-scale insight into the proton migration mechanisms in perovskites and offer practical guidance for optimizing and designing advanced proton-conducting electrolytes.