Calcium metal batteries(CMBs),utilizing calcium(Ca)as anodes,offer great potential for next-generation high-energy density battery technologies.However,Ca plating/stripping at room temperature(r.t.)is severely impeded...Calcium metal batteries(CMBs),utilizing calcium(Ca)as anodes,offer great potential for next-generation high-energy density battery technologies.However,Ca plating/stripping at room temperature(r.t.)is severely impeded by the formation of ion-insulating passivation layers.Constructing artificial protective layers that can effectively transport Ca^(2+)on Ca metal is crucial for realizing practical CMBs.Nonetheless,identifying a suitable candidate that is both highly ionic conductive(>10^(-4) S cm^(-1) at r.t.)and electrically insulating remains a formidable challenge.Ionic covalent organic frameworks(iCOFs)represent a distinctive class of porous,crystalline polymers containing ionic moieties to facilitate ion conduction in batteries.In this study,we introduce,for the first time,single-ion conductive sulfonate iCOFs with a Ca^(2+) transference number of 0.95 and ionic conductivity of 2.2310-4 S cm^(-1) at r.t.as artificial protective layers for the Ca metal anode.This iCOF protective layer promotes uniform Ca deposition and effective anticorrosion of modified anodes.As a result,full cells equipped with iCOF-protective Ca anodes and polyaniline cathodes demonstrated stable operation up to 75 cycles with high energy density.Our work facilitates the attainment of high-performance CMBs by the construction of iCOF protective layers.展开更多
基金Research Grants Council of the Hong Kong SAR Government,Grant/Award Numbers:16306921,16306022,15305022,C6047-23GFShanghai Municipal Natural Science Foundation,Grant/Award Number:22ZR1433400Hong Kong Polytechnic University,G-UARH,Grant/Award Number:1-BBR0。
文摘Calcium metal batteries(CMBs),utilizing calcium(Ca)as anodes,offer great potential for next-generation high-energy density battery technologies.However,Ca plating/stripping at room temperature(r.t.)is severely impeded by the formation of ion-insulating passivation layers.Constructing artificial protective layers that can effectively transport Ca^(2+)on Ca metal is crucial for realizing practical CMBs.Nonetheless,identifying a suitable candidate that is both highly ionic conductive(>10^(-4) S cm^(-1) at r.t.)and electrically insulating remains a formidable challenge.Ionic covalent organic frameworks(iCOFs)represent a distinctive class of porous,crystalline polymers containing ionic moieties to facilitate ion conduction in batteries.In this study,we introduce,for the first time,single-ion conductive sulfonate iCOFs with a Ca^(2+) transference number of 0.95 and ionic conductivity of 2.2310-4 S cm^(-1) at r.t.as artificial protective layers for the Ca metal anode.This iCOF protective layer promotes uniform Ca deposition and effective anticorrosion of modified anodes.As a result,full cells equipped with iCOF-protective Ca anodes and polyaniline cathodes demonstrated stable operation up to 75 cycles with high energy density.Our work facilitates the attainment of high-performance CMBs by the construction of iCOF protective layers.
