The exploration of bifunctional electrocatalysts with high catalytic activity and long-term durability for low-temperature Zn-air batteries(ZABs)is an ongoing challenge.Here,quintet-shelled hollow spheres,P-doped mult...The exploration of bifunctional electrocatalysts with high catalytic activity and long-term durability for low-temperature Zn-air batteries(ZABs)is an ongoing challenge.Here,quintet-shelled hollow spheres,P-doped multi-layer Co_(3)O_(4)(PM-Co_(3)O_(4)),with enriched oxygen vacancies are prepared by thermally induced mass relocation and a simple phosphating process.Various advanced characterizations reveal P anion-induced effects on internal electronic structure and local coordination environment.The finite element method elucidates that the complex multi-layer spherical nanostructure is conducive to the transport and diffusion of OH-and O_(2).Benefiting from its unique structural features and abundant oxygen vacancies,the well-designed PM-Co_(3)O_(4) presents small reversible oxygen overpotential for catalyzing oxygen reduction/evolution reactions.Accordingly,the fabricated low-temperature ZABs based on PM-Co_(3)O_(4) as air-cathode exhibit high power density(20.8 mW·cm^(-2))and long-term stability(over 600 cycles)at the ultra-low temperature of-40℃,outperforming state-of-art Pt/C+IrO_(2)-based ZABs.Furthermore,the dynamic evolution mechanism of cobalt oxide catalysts during ZAB operation is elucidated.This work provides a guideline to design efficient electrocatalysts with regulated electronic configurations and exquisite nano-/microstructures for ZABs under extreme working conditions.展开更多
基金supported by the Natural Science Foundation of Guangdong Province(Nos.2021A1515010504,2022A1515010049)the National Natural Science Foundation of China(Nos.21706090,52172202,51872124)+1 种基金the Major Technological Innovation Project of Hubei Science and Technology Department(No.2019AAA164)the Natural Science Foundation of Guangzhou(No.201904010049).
文摘The exploration of bifunctional electrocatalysts with high catalytic activity and long-term durability for low-temperature Zn-air batteries(ZABs)is an ongoing challenge.Here,quintet-shelled hollow spheres,P-doped multi-layer Co_(3)O_(4)(PM-Co_(3)O_(4)),with enriched oxygen vacancies are prepared by thermally induced mass relocation and a simple phosphating process.Various advanced characterizations reveal P anion-induced effects on internal electronic structure and local coordination environment.The finite element method elucidates that the complex multi-layer spherical nanostructure is conducive to the transport and diffusion of OH-and O_(2).Benefiting from its unique structural features and abundant oxygen vacancies,the well-designed PM-Co_(3)O_(4) presents small reversible oxygen overpotential for catalyzing oxygen reduction/evolution reactions.Accordingly,the fabricated low-temperature ZABs based on PM-Co_(3)O_(4) as air-cathode exhibit high power density(20.8 mW·cm^(-2))and long-term stability(over 600 cycles)at the ultra-low temperature of-40℃,outperforming state-of-art Pt/C+IrO_(2)-based ZABs.Furthermore,the dynamic evolution mechanism of cobalt oxide catalysts during ZAB operation is elucidated.This work provides a guideline to design efficient electrocatalysts with regulated electronic configurations and exquisite nano-/microstructures for ZABs under extreme working conditions.
