arXiv subjects

Jiajun Linghu

Publications and source records attributed to Jiajun Linghu.

3 recordsLinked to original sources

arXiv2025

Lattice-Distortion-Mediated Proton Pairing and Trapping in Solid State Oxides

Experiments have evidenced proton pairing in Y-doped BaZrO3. However, the nature of proton pairing and its impact on conduction remain insufficiently understood theoretically. Here, through quantitative computational analysis of proton-proton interactions in Y-doped BaZrO3, we identify lattice-distortion-mediated elastic interaction as the key factor determining whether two protons form a stable pair or exhibit net repulsion. When a proton resides at an inward-bending distortion site induced by another proton, the resulting net repulsive interaction leads to an unstable configuration. In contrast, the proton tends to be trapped at a nearby outward-bending site that favors the formation of a stable proton pair. Moreover, the site where the two protons form the lowest-energy configuration also corresponds to a proton trapping site. By calculating the long-range diffusion pathways accessible to protons under different local environments in both single- and two-proton cases, we find that the range of rate-limiting barriers is 0.24-0.45 eV for two-proton conduction and 0.19-0.39 eV for single-proton conduction. The higher and more experimentally consistent barriers in the two-proton pathways indicate that the proton trapping effect induced by pairing hinders proton conduction. Our study elucidates the multi-proton diffusion mechanism, providing a theoretical foundation for the experimental design of electrolytes with enhanced proton conductivity.

cond-mat.mtrl-sci↗

arXiv2025

In-depth Investigation of Conduction Mechanism on Defect-induced Proton-conducting Electrolytes BaHfO$_3$

This study utilizes first-principles computational methods to comprehensively analyze the impact of A-site doping on the proton conduction properties of BaHfO$_3$. The goal is to offer theoretical support for the advancement of electrolyte materials for solid oxide fuel cells. Our research has uncovered that BaHfO$_3$ demonstrates promising potential for proton conduction, with a low proton migration barrier of $0.28$ eV, suggesting efficient proton conduction can be achieved at lower temperatures. Through A-site doping, particularly with low-valence-state ions and the introduction of Ba vacancies, we can effectively decrease the formation energy of oxygen vacancies ($ E_{\text{vac}} $), leading to an increase in proton concentration. Additionally, our study reveals that the primary mechanism for proton migration in BaHfO$_3$ is the Grotthuss mechanism rather than the vehicle mechanism. Examination of the changes in lattice parameters during proton migration indicates that while doping or vacancy control strategies do not alter the mode of H$^+$ migration, they do influence the migration pathway and barrier. These findings provide valuable insights into optimizing the proton conduction properties of BaHfO$_3$ through A-site doping and lay a solid theoretical foundation for the development of novel, highly efficient solid oxide fuel cell electrolyte materials.

cond-mat.mtrl-sci↗

arXiv2025

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~\AA, 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.

cond-mat.mtrl-sci↗