Band Structure and Spin‐State‐Induced Electronic Configuration Regulation for Efficient Sulfur Redox Reaction

• Published in: Advanced functional materials 2024-11
• Main Authors: Zhou, Fei, Gong, Zhiqi, Wang, Renheng, Guo, Mengran, Zeng, Rong, Li, Yun, Xiao, Zhe, Qie, Long, Liu, Jianwen
• Format: Article
• Language: English
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202417730

Deciphering the relationship between electron configuration and catalytic activity is crucial for designing electrocatalysts that improve the efficient conversion of lithium polysulfides (LiPSs). In this study, amorphous ZnAl 2 O 4 (referred to as A‐ZnAl 2 O 4 ) is designed with a high oxygen vacancy concentration. Experimental and theoretical analysis confirm that the Zn tetrahedral sites are sufficiently exposed, and the catalytic activity is significantly enhanced due to a narrow bandgap and a high spin state achieved through low coordination numbers and a disordered structure. Both the enhancement in electron transfer efficiency and reduction in reaction energy barriers accelerate the multi‐phase transformation of LiPSs, resulting in impressive electrochemical performance with a capacity retention rate of 93.9% after 800 cycles at a high current density of 4 C. And the pouch battery with high sulfur loading of 4.5 mg cm −2 and lean electrolyte at 8 µL mg −1 exhibits high discharge capacity and stable cycling. This research deciphers the amorphization on modulating electronic structures to achieve enhanced electrocatalytic activity, providing a general strategy for designing unique atomic‐scale band structures and spin states in multifunctional electrocatalysts.