Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but ...Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.展开更多
Facilitating sulfur reduction reaction(SRR)is a promising pathway to tackle the polysulfide shuttle effect and enhance the electrochemical performance of lithium-sulfur(Li-S)batteries.Catalysts with a solo active site...Facilitating sulfur reduction reaction(SRR)is a promising pathway to tackle the polysulfide shuttle effect and enhance the electrochemical performance of lithium-sulfur(Li-S)batteries.Catalysts with a solo active site can reduce a reaction barrier of a certain transition-intermediate,but the linear scaling relationship between multi-intermediates still obstructs overall SRR.Herein,we construct tandem Co–O dual sites with accelerating SRR kinetics by loading highly dispersed cobalt sulfide clusters on halloysite.This catalyst features Co with upshifted d-orbital and O with downshifted p-orbital,which cooperatively adsorb long-chain polysulfide and dissociate an S–S bond,thus achieving both optimal adsorption–desorption strength and reduced conversion energy barrier of multi-intermediates in SRR.The Li-S coin batteries using the electrocatalyst endows a high specific capacity of 1224.3 m Ah g^(-1)at 0.2 C after 200cycles,and enhances cycling stability with a low-capacity decay rate of 0.03%per cycle at 1 C after1000 cycles.Moreover,the strategy of the tandem Co–O dual sites is further verified in a practical Li-S pouch battery that realizes 1014.1 m Ah g^(-1)for 100 cycles,which opens up a novel avenue for designing electrocatalysts to accelerate multi-step reactions.展开更多
基金financially supported by the National Natural Science Foundation of China (22279122,52042403)the Zhejiang Provincial Natural Science Foundation of China (LZ22B030004)+2 种基金the Ministry of Education,Singapore,under its Academic Research Fund Tier 1 (RG10/22)the National Institute of Education,Singapore,under its Academic Research Fund (RI 1/21 EAH)National Institute of Education,Singapore,under its Start-Up Grant (NIE-SUG4/20AHX)。
文摘Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.
基金supported by the National Science Fund for Distinguished Young Scholars(51225403)the National Natural Science Foundation of China(52042403)+3 种基金the National Postdoctoral Program for Innovative Talents(BX2021276)the China Postdoctoral Science Foundation(2020M682519)the Strategic Priority Research Program of Central South University(ZLXD2017005)the“CUG Scholar"Scientific Research Funds at China University of Geosciences(Wuhan)(Project No.20222020110)。
文摘Facilitating sulfur reduction reaction(SRR)is a promising pathway to tackle the polysulfide shuttle effect and enhance the electrochemical performance of lithium-sulfur(Li-S)batteries.Catalysts with a solo active site can reduce a reaction barrier of a certain transition-intermediate,but the linear scaling relationship between multi-intermediates still obstructs overall SRR.Herein,we construct tandem Co–O dual sites with accelerating SRR kinetics by loading highly dispersed cobalt sulfide clusters on halloysite.This catalyst features Co with upshifted d-orbital and O with downshifted p-orbital,which cooperatively adsorb long-chain polysulfide and dissociate an S–S bond,thus achieving both optimal adsorption–desorption strength and reduced conversion energy barrier of multi-intermediates in SRR.The Li-S coin batteries using the electrocatalyst endows a high specific capacity of 1224.3 m Ah g^(-1)at 0.2 C after 200cycles,and enhances cycling stability with a low-capacity decay rate of 0.03%per cycle at 1 C after1000 cycles.Moreover,the strategy of the tandem Co–O dual sites is further verified in a practical Li-S pouch battery that realizes 1014.1 m Ah g^(-1)for 100 cycles,which opens up a novel avenue for designing electrocatalysts to accelerate multi-step reactions.
