Reversible proton ceramic electrochemical cells (R-PCECs) have emerged as a promising solution for sustainable energy conversion and storage at intermediate temperatures. However, the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics at the air electrodes of R-PCECs limit the cell performance. To achieve improved ORR/OER catalytic performance, we propose a practical approach of strategic anion engineering on the oxygen site of air electrode materials. Specifically, the popular triple H⁺/e⁻/O²⁻ conducting oxide (TCO) Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) is selected to enhance the limiting H⁺/O²⁻ generation and migration processes as an efficient air electrode for R-PCECs. By introducing different electronegative elements (F and Cl) to weaken metal-oxygen bonds (M-O), the oxygen chemical environment of the electrode material was optimized, thereby promoting surface oxygen exchange and O²⁻/H⁺ bulk migration. The resulting Ba_0.5Sr_0.5Co_0.8Fe_0.2O_2.9-σF_0.1 electrode exhibits enhanced proton uptake/mobility and catalytic activity for ORR and OER, as well as improved stability. This research offers a rational design strategy for engineering high-performance R-PCEC air electrodes with enhanced operating stability for efficient and sustainable energy conversion and storage.

可逆质子陶瓷电化学电池（R-PCEC）已成为中间温度下可持续能源转换和存储的有前途的解决方案。然而，R-PCEC 空气电极缓慢的氧还原反应（ORR）和析氧反应（OER）动力学限制了电池性能。为了提高 ORR/OER 催化性能，我们提出了一种在空气电极材料的氧位点进行战略阴离子工程的实用方法。具体而言，选择流行的三重H ⁺ /e ^- /O ²⁻导电氧化物（TCO）Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _3−δ（BSCF）来增强限制性H ⁺ /O ²⁻生成和迁移过程。作为 R-PCEC 的高效空气电极。通过引入不同的电负性元素（F和Cl）来弱化金属氧键（MO），优化电极材料的氧化学环境，从而促进表面氧交换和O 2− /H ⁺本体^迁移。所得Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _2.9-σ F _0.1电极表现出增强的质子吸收/迁移率以及ORR和OER的催化活性，以及​​改进的稳定性。这项研究为工程高性能 R-PCEC 空气电极提供了合理的设计策略，增强了运行稳定性，实现高效、可持续的能量转换和存储。