High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unpa...High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unparalleled performance,the relationships between multiple active sites and reaction intermediates are still obscure.Here,enlightened by theoretical screening,we tailor a high-entropy perovskite fluoride(KCoMnNiMgZnF_(3)-HEC)with various active sites to overcome the limitations of conventional catalysts in redox process.The entropy effect modulates the d-band center and d orbital occupancy of active centers,which optimizes the d–p hybridization between catalytic sites and key intermediates,enabling a moderate adsorption of LiO_(2)and thus reinforcing the reaction kinetics.As a result,the Li–O2 battery with KCoMnNiMgZnF_(3)-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability,preceding majority of traditional catalysts reported.These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.展开更多
基金P.G.acknowledges the financial support from the Youth Foundation of Shandong Natural Science Foundation(No.ZR2023OB230)National Natural Science Foundation(No.22309035)Double First-class Discipline Construction Fund Project of Harbin Institute of Technology at Weihai(No.2023SYLHY11).
文摘High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unparalleled performance,the relationships between multiple active sites and reaction intermediates are still obscure.Here,enlightened by theoretical screening,we tailor a high-entropy perovskite fluoride(KCoMnNiMgZnF_(3)-HEC)with various active sites to overcome the limitations of conventional catalysts in redox process.The entropy effect modulates the d-band center and d orbital occupancy of active centers,which optimizes the d–p hybridization between catalytic sites and key intermediates,enabling a moderate adsorption of LiO_(2)and thus reinforcing the reaction kinetics.As a result,the Li–O2 battery with KCoMnNiMgZnF_(3)-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability,preceding majority of traditional catalysts reported.These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.
