Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growt...Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.展开更多
The interfacial structure and adsorption mechanism of imidazolium-based ionic liquids(ILs)on Au(111)surface were investigated via first-principles calculation.Electron density analysis and Bader charge analysis were u...The interfacial structure and adsorption mechanism of imidazolium-based ionic liquids(ILs)on Au(111)surface were investigated via first-principles calculation.Electron density analysis and Bader charge analysis were used to explore the electronic structure of Au(111)-ILs interface.Computations show that the alkyl chain length and anions play a significant role in designing Au(111)-ILs interfacial structure.On the one hand,the stability of interface and adsorption energy tend to be enhanced as the alkyl chain length increases.It attributes to the methylene group of alkyl chain which could easily anchor on the gold interface.On the other hand,the difference in anions makes the adsorption behavior quite different.The adsorption energy follows the order:[C_(n)mim][Br]>[C_(n)mim][Cl]>[Cnmim][TFSA]>[C_(n)mim][OAc]>[C_(n)mim][PF6]>[C_(n)mim][BF_(4)].The nonfluorinated ILs(containing Br,Cl,and O atoms of anions)always have a drastic charge transfer among gold-ILs interface.However,the larger van der Waals(vdWs)volumes of the fluorinated anions have a more diffused electron density which lead to the relatively weak interaction.To sum up,a detailed and systematic investigation of the variation of anions and alkyl chain length of ILs which will affect the interfacial structure is fully studied.The above study could be helpful to understand electrode-electrolyte microscopic interface and design of functional materials for energy storage.展开更多
基金support from the National Natural Science Foundation of China(22209089,22178187)Natural Science Foundation of Shandong Province(ZR2022QB048,ZR2021MB006)+2 种基金Excellent Youth Science Foundation of Shandong Province(Overseas)(2023HWYQ-089)the Taishan Scholars Program of Shandong Province(tsqn201909091)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.
基金supported by Taishan Scholars Program of Shandong Province(tsqn201909091)National Natural Science Foundation of China(U1704251,21722610)the High-Grade Talents Plan of Qingdao University.
文摘The interfacial structure and adsorption mechanism of imidazolium-based ionic liquids(ILs)on Au(111)surface were investigated via first-principles calculation.Electron density analysis and Bader charge analysis were used to explore the electronic structure of Au(111)-ILs interface.Computations show that the alkyl chain length and anions play a significant role in designing Au(111)-ILs interfacial structure.On the one hand,the stability of interface and adsorption energy tend to be enhanced as the alkyl chain length increases.It attributes to the methylene group of alkyl chain which could easily anchor on the gold interface.On the other hand,the difference in anions makes the adsorption behavior quite different.The adsorption energy follows the order:[C_(n)mim][Br]>[C_(n)mim][Cl]>[Cnmim][TFSA]>[C_(n)mim][OAc]>[C_(n)mim][PF6]>[C_(n)mim][BF_(4)].The nonfluorinated ILs(containing Br,Cl,and O atoms of anions)always have a drastic charge transfer among gold-ILs interface.However,the larger van der Waals(vdWs)volumes of the fluorinated anions have a more diffused electron density which lead to the relatively weak interaction.To sum up,a detailed and systematic investigation of the variation of anions and alkyl chain length of ILs which will affect the interfacial structure is fully studied.The above study could be helpful to understand electrode-electrolyte microscopic interface and design of functional materials for energy storage.
