Protonic ceramic fuel cells (PCFCs) have generated significant interest due to their weak temperature dependence and efficient energy conversion. However, traditional cathode materials show poor electrocatalytic activity at a low operating temperature due to their intrinsically slow proton diffusion, which is a long-standing issue that limits the output performance of PCFCs. Herein, the strategy of fluorinating a perovskite cathode is proposed for promoting proton transfer within the bulk of the cathode. This strategy is demonstrated in a fluorinated BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3−δ (BCFZY) perovskite, which reveals a reduced polarization resistance and enhanced PCFC output performance, superior to those of newly reported PCFCs. Combing the experimental characterization and theoretical calculations, we found that the performance improvement was ascribed to the strong inductive effect of F⁻, which can increase the polarity the M−O bonding and decrease the O···H interaction, thus boosting the production of protonic defects and increasing the protonic diffusion coefficient.

质子陶瓷燃料电池（PCFC）由于其较弱的温度依赖性和高效的能量转换而引起了极大的兴趣。然而，传统的正极材料由于质子扩散缓慢而在低工作温度下表现出较差的电催化活性，这是一个长期存在的问题，限制了 PCFC 的输出性能。在此，提出了氟化钙钛矿阴极的策略，以促进阴极主体内的质子转移。该策略在氟化 BaCo _0.4 Fe _0.4 Zr _0.1 Y _0.1 O _3-δ（BCFZY）钙钛矿，显示出降低的极化电阻和增强的 PCFC 输出性能，优于新报道的 PCFC。结合实验表征和理论计算，我们发现性能的提高归因于 F ^-的强感应效应，它可以增加 M-O 键的极性并减少 O···H 相互作用，从而促进生产质子缺陷和增加质子扩散系数。