Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-it...Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.展开更多
基金supported by the National Natural Science Foundation of China (21878340)supported in part by the High-Performance Computing Center of Central South University
文摘Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.
