Polaron-mediated metal-insulator transition and proton conduction in hydrogenated nickelate perovskites

Abstract

Nickel-based perovskites, owing to their spontaneous hydrogen uptake and the dramatic increase in resistivity upon hydrogenation, have emerged as promising candidates for proton-conducting fuel cell electrolytes. However, the mechanism of the hydrogen-induced metal-insulator transition (MIT) in rare-earth nickelates remains under debate, particularly regarding whether the doped electrons occupy Ni e$_g$ states or O 2p ligand hole states. Here, we reveal a comprehensive MIT mechanism using first-principles calculations on NdNiO$_3$: the electrons introduced by hydrogen doping occupy the O 2p ligand hole states of the Ni-O hybridized d$_8$L configuration, promoting electron-polaron formation. The resulting electron polarons, together with proton polarons, weaken the Ni-O hybridization and thereby drive the originally itinerant Ni e$_g$ electrons toward localization. This generates a local d8 (t$_{2g}$$^6$e$_g$$^2$) electronic configuration, leading to a Mott transition. In addition, we also find that compared with NdNiO$_3$, SmNiO$_3$ with a smaller A-site ionic radius more readily absorbs hydrogen but exhibits weaker proton diffusion capability. Hydrogenation promotes proton permeation along the [001] direction via the intraoctahedral transfer, whereas the overall proton diffusivity is reduced. These results provide guidance for experimental screening of strongly correlated oxides as electrolyte materials and offer theoretical insights for enhancing proton conductivity in rare-earth nickelates.