Interface and Phase Synergy in Hierarchically Porous Co@(Co–Mn) 3 O 4– x for High-Efficiency and Durable Rechargeable Zn–Air Batteries

作者：Kayla S. Smith, Christabel Adjah‐Tetteh, Zizhou He, Gang Yang, Yudong Wang, Stoyan Bliznakov, Radenka Marić, Nengneng Xu, Xiao‐Dong Zhou · 发表于：The Journal of Physical Chemistry C · 年份：2025 · DOI：10.1021/acs.jpcc.5c03413 · 被引用次数：25 · 研究领域：Advanced battery technologies research、Supercapacitor Materials and Fabrication、Electrocatalysts for Energy Conversion

The development of highly active and durable bifunctional electrocatalysts remains a key challenge in advancing rechargeable Zn–air battery technology. In this work, we report a synergistically integrated metal cluster on an oxide catalyst, Co@(Mn 0.6 Co 0.4 ) 3 O 4– x, to address this issue. The catalyst was synthesized through the hydrogen reduction of a spinel-structured (Mn 0.4 Co 0.6 ) 3 O 4 precursor. The reduction process yields a finely tuned multiphase composition, consisting of metallic Co and oxygen-deficient (Mn 0.6 Co 0.4 ) 3 O 4– x spinel, while resulting in a nanomicro porous architecture. This engineered structure provides synergistic benefits: (1) metallic Co enhances electrical conductivity, (2) oxygen-deficient spinel domains create abundant active sites, and (3) the hierarchical porous framework improves mass transport. As a result, Co@(Mn 0.6 Co 0.4 ) 3 O 4– x exhibits high bifunctional oxygen activity with a low overpotential, 460.5 mV at 10 mA cm –2 for the oxygen evolution reaction (OER), and a favorable four-electron oxygen reduction reaction (ORR) pathway ( n = ∼3.94). It also shows a low bifunctional Δ E of 0.97 V and robust stability. In actual applications, the Co@(Mn 0.6 Co 0.4 ) 3 O 4– x cathode-based Zn–air battery demonstrates an open-circuit voltage of 1.48 V and a peak power density of 299.9 mW cm –2, with long-term discharge for 98 h and stable cycling over 460 cycles. Further analysis reveals that in primary battery mode, cathode performan...