Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical b...Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical behaviors,yet has not been unraveled.Here we propose an NH_(4)^(+)-modulated cationic solvation strategy to optimize cathodic spatial charge distribution and achieve dynamic Zn^(2+)/NH_(4)^(+)co-storage for boosting Zinc hybrid capacitors.Owing to the hierarchical cationic solvated structure in hybrid Zn(CF_(3)SO_(3))_(2)–NH_4CF_(3)SO_(3)electrolyte,high-reactive Zn^(2+)and small-hydrate-sized NH_4(H_(2)O))(4)^(+)induce cathodic interfacial Helmholtz plane reconfiguration,thus effectively enhancing the spatial charge density to activate 20%capacity enhancement.Furthermore,cathodic interfacial adsorbed hydrated NH_(4)^(+)ions afford high-kinetics and ultrastable C···H(NH_(4)^(+))charge storage process due to a much lower desolvation energy barrier compared with heavy and rigid Zn(H_(2)O)_6^(2+)(5.81 vs.14.90 eV).Consequently,physical uptake and multielectron redox of Zn^(2+)/NH_(4)^(+)in carbon cathode enable the zinc capacitor to deliver high capacity(240 mAh g^(-1)at 0.5 A g^(-1)),large-current tolerance(130 mAh g^(-1)at 50 A g^(-1))and ultralong lifespan(400,000cycles).This study gives new insights into the design of cathode–electrolyte interfaces toward advanced zinc-based energy storage.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111 and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300 and 19DZ2271500)+3 种基金China Postdoctoral Science Foundation(2022M712402)Shanghai Rising-Star Program(23YF1449200)Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(22120210529 and 2023-3-YB-07)。
文摘Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical behaviors,yet has not been unraveled.Here we propose an NH_(4)^(+)-modulated cationic solvation strategy to optimize cathodic spatial charge distribution and achieve dynamic Zn^(2+)/NH_(4)^(+)co-storage for boosting Zinc hybrid capacitors.Owing to the hierarchical cationic solvated structure in hybrid Zn(CF_(3)SO_(3))_(2)–NH_4CF_(3)SO_(3)electrolyte,high-reactive Zn^(2+)and small-hydrate-sized NH_4(H_(2)O))(4)^(+)induce cathodic interfacial Helmholtz plane reconfiguration,thus effectively enhancing the spatial charge density to activate 20%capacity enhancement.Furthermore,cathodic interfacial adsorbed hydrated NH_(4)^(+)ions afford high-kinetics and ultrastable C···H(NH_(4)^(+))charge storage process due to a much lower desolvation energy barrier compared with heavy and rigid Zn(H_(2)O)_6^(2+)(5.81 vs.14.90 eV).Consequently,physical uptake and multielectron redox of Zn^(2+)/NH_(4)^(+)in carbon cathode enable the zinc capacitor to deliver high capacity(240 mAh g^(-1)at 0.5 A g^(-1)),large-current tolerance(130 mAh g^(-1)at 50 A g^(-1))and ultralong lifespan(400,000cycles).This study gives new insights into the design of cathode–electrolyte interfaces toward advanced zinc-based energy storage.
