Guan Hao-Min, Cai Zhi-Peng, Wu Xue-Yan, Wang Kai-Xue, Chen Jie-Sheng
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, P.R. China.
Zhiyuan College, Shanghai Jiao Tong University, Shanghai, 200240, P.R. China.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202509132. doi: 10.1002/anie.202509132. Epub 2025 Jul 9.
Lithium-oxygen batteries (LOBs) require fast oxygen conversion kinetics to achieve good cycling performance and high energy efficiency. In the text of catalysts for LOBs, the Lewis basicity of lattice oxygens (O) in common transition metal oxides is often underestimated due to the weak electron donor characteristic of O. In this work, a new spinel-type high entropy oxide with Lewis basicity (LB-HEO) was synthesized through a Joule-heating method. O was activated by regulating the tetrahedral site-O-octahedral site (M-O-M) units in the spinel-type HEO, enhancing the LB. Used as a cathode catalyst for LOBs, LB-HEO could attract Li and increase the disorder in discharge product, lithium peroxide (LiO), promoting the delithiation process and the interfacial charge transfer at the LB-HEO|LiO interface. The activation energy of interfacial charge transfer was significantly reduced from 63.5 to 22.4 kJ mol. As a result, a low charging overpotential of 0.97 V and a long cycling lifespan of 135 cycles at 100 mA g were achieved with a capacity limitation of 1000 mAh g. The strategy based on the regulation of Li behavior through its interaction with Lewis bases provides a promising prospect for the design of non-noble metal catalysts for high-performance LOBs.
锂氧电池（LOBs）需要快速的氧转化动力学来实现良好的循环性能和高能效。在LOBs的催化剂文献中，由于晶格氧（O）的电子供体特性较弱，常见过渡金属氧化物中晶格氧的路易斯碱性常常被低估。在这项工作中，通过焦耳加热法合成了一种具有路易斯碱性的新型尖晶石型高熵氧化物（LB-HEO）。通过调节尖晶石型HEO中的四面体位置-O-八面体位置（M-O-M）单元来激活O，增强路易斯碱性。用作LOBs的阴极催化剂时，LB-HEO能够吸引Li并增加放电产物过氧化锂（LiO）中的无序度，促进脱锂过程以及LB-HEO|LiO界面处的界面电荷转移。界面电荷转移的活化能从63.5显著降低至22.4 kJ mol。结果，在100 mA g的电流密度下，容量限制为1000 mAh g时，实现了0.97 V的低充电过电位和135次循环的长循环寿命。基于通过Li与路易斯碱的相互作用来调节Li行为的策略，为高性能LOBs的非贵金属催化剂设计提供了广阔的前景。
