Mn Additive Improves Zr Grain Boundary Diffusion for Sintering of a Y-Doped BaZrO₃ Proton Conductor

Yttrium-doped barium zirconate (BZY) has garnered attention as a protonic conductor in intermediate-temperature electrolysis and fuel cells due to its high bulk proton conductivity and excellent chemical stability. However, the performance of BZY can be further enhanced by reducing the concentration and resistance of grain boundaries. In this study, we investigate the impact of manganese (Mn) additives on the sinterability and proton conductivity of Y-doped BaZrO₃ (BZY). By employing a combinatorial pulsed laser deposition (PLD) technique, we synthesized BZY thin films with varying Mn concentrations and sintering temperatures. Our results revealed a significant enhancement in sinterability as Mn concentrations increased, leading to larger grain sizes and lower grain boundary concentrations. These improvements can be attributed to the elevated grain boundary diffusion of zirconium (Zr) cations, which enhances material densification. We also observed a reduction in Goldschmidt's tolerance factor with increased Mn substitution, which can improve proton transport. The high proton conduction of BZY with Mn additives in low-temperature and wet hydrogen environments makes it a promising candidate for protonic ceramic electrolysis cells and fuel cells. Our findings not only advance the understanding of Mn additives in BZY materials but also demonstrate a high-throughput combinatorial thin film approach to select additives for other perovskite materials with importance in mass and charge transport applications.