The rechargeable aluminum batteries(RAB)have shown great potential for energy storage applications due to their low-cost and superior volumetric capacity.However,the battery performances are far from satisfactory owin...The rechargeable aluminum batteries(RAB)have shown great potential for energy storage applications due to their low-cost and superior volumetric capacity.However,the battery performances are far from satisfactory owing to the poor kinetics of electrode reactions,including the solid-state ionic diffusion and interfacial charge transfer.The charge transfer reaction,typically the cation desolvation at the interface(Helmholtz plane),is crucial for determining the interfacial charge transfer,which induces the solvent effect in batteries but has not been explored in RABs.Herein,we provide a comprehensive understanding of solvent effects on interface kinetics and electrochemical performance of RAB by analyzing the desolvation process and charge transfer energy barrier.The pivotal role of solvent effects is confirmed by the successful application of Al(OTF)_(3)-H_(2)O electrolyte,which displays easy desolvation,low charge transfer resistance,and thus superior Al-ion storage performance over other electrolytes in our studies.In addition,based on the strong correlation between the calculated desolvation energy and charge transfer energy barrier,the calculation of dissociation energy of ion-solvent complex is demonstrated as an efficient index for designing electrolytes.The in-depth understanding of solvent effects provides rational guidance for new electrolyte and RAB design.展开更多
The stability of organic radicals in ambient condition is important for their practical application.During the development of organic radical chemistry,the electron-withdrawing and steric hindrance groups are usually ...The stability of organic radicals in ambient condition is important for their practical application.During the development of organic radical chemistry,the electron-withdrawing and steric hindrance groups are usually introduced to improve the stability of radicals via reducing the reactivity of radicals with oxygen in air.Herein,the electron-withdrawing carbonyl groups are introduced to construct a planar aromatic oxalic acid radical(IDF-Og)with two-dimensional electron spin pan structure.Interestingly,IDF-Og exhibited a low optical bandgap of 0.91 eV in film,however,the multiple quinone resonance structures between electron-withdrawing ketone and phenol radicals contribute to the high stability of open-shell radical IDF-Og without protection of large steric hindrance groups.Under the irradiation of 808 nm(1.2 W.cm^(-2)),IDF-Og reaches 147 c in powder state.This work provides an efficient synthesis route for the open-shell electron spin pan system,which is different from the famous fullerene,carbon nanotube and graphene.The electron spin pan can be extended to spin tube or spin sphere system based on the design strategy of aromatic inorganic acid radicals in future.展开更多
基金This work was supported by the National Natural Science Foundation of China(22075028).
文摘The rechargeable aluminum batteries(RAB)have shown great potential for energy storage applications due to their low-cost and superior volumetric capacity.However,the battery performances are far from satisfactory owing to the poor kinetics of electrode reactions,including the solid-state ionic diffusion and interfacial charge transfer.The charge transfer reaction,typically the cation desolvation at the interface(Helmholtz plane),is crucial for determining the interfacial charge transfer,which induces the solvent effect in batteries but has not been explored in RABs.Herein,we provide a comprehensive understanding of solvent effects on interface kinetics and electrochemical performance of RAB by analyzing the desolvation process and charge transfer energy barrier.The pivotal role of solvent effects is confirmed by the successful application of Al(OTF)_(3)-H_(2)O electrolyte,which displays easy desolvation,low charge transfer resistance,and thus superior Al-ion storage performance over other electrolytes in our studies.In addition,based on the strong correlation between the calculated desolvation energy and charge transfer energy barrier,the calculation of dissociation energy of ion-solvent complex is demonstrated as an efficient index for designing electrolytes.The in-depth understanding of solvent effects provides rational guidance for new electrolyte and RAB design.
基金supported by the Natural Science Foundation of China(22375065,51973063).
文摘The stability of organic radicals in ambient condition is important for their practical application.During the development of organic radical chemistry,the electron-withdrawing and steric hindrance groups are usually introduced to improve the stability of radicals via reducing the reactivity of radicals with oxygen in air.Herein,the electron-withdrawing carbonyl groups are introduced to construct a planar aromatic oxalic acid radical(IDF-Og)with two-dimensional electron spin pan structure.Interestingly,IDF-Og exhibited a low optical bandgap of 0.91 eV in film,however,the multiple quinone resonance structures between electron-withdrawing ketone and phenol radicals contribute to the high stability of open-shell radical IDF-Og without protection of large steric hindrance groups.Under the irradiation of 808 nm(1.2 W.cm^(-2)),IDF-Og reaches 147 c in powder state.This work provides an efficient synthesis route for the open-shell electron spin pan system,which is different from the famous fullerene,carbon nanotube and graphene.The electron spin pan can be extended to spin tube or spin sphere system based on the design strategy of aromatic inorganic acid radicals in future.
