Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds...Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds with unique structures.In recent years,owing to their abundant physicochemical properties(including high ionic conductivity and reversible redox activity),POMs have shown great potential in becoming a new generation of solid-state electrolytes.In this review,an overview is investigated about how POMs have evolved as ion-conducting materials from basic research to novel solid-state electrolytes in energy devices.First,some expressive POM-based ion-conducting materials in recent years are introduced and classified,mainly inspecting their structural and functional relationship.After that,it is further focused on the application of these ionconducting electrolytes in the fields of proton exchange membranes,supercapacitors,and ion batteries.In addition,some properties of POMs(such as inherent dimension,capable of forming stable hydrogen bonds,and reversible bonding to water molecules)enable these functional POM-based electrolytes to be employed in innovative applications such as ion selection,humidity sensing,and smart materials.Finally,some fundamental recommendations are given on the current opportunities and challenges of POM-based ion-conducting electrolytes.展开更多
In order to sustainably transform N2 to ammonia(NRR)using electrocatalysts under mild ambient condition,it is urgent to design and develop non-nobel metal nanocatalysts that are inexpensive and suitable for mass-produ...In order to sustainably transform N2 to ammonia(NRR)using electrocatalysts under mild ambient condition,it is urgent to design and develop non-nobel metal nanocatalysts that are inexpensive and suitable for mass-production.Herein,a calcium metalate catalyst CaCoO_(x)with oxygen vacancies was synthesized and used as an electrocatalyst for NRR for the first time,whose morphology can be controlled by the calcination temperature and the heating rate.Under the optimal conditions,the CaCoO_(x)catalyst achieved the yield of nitrogen conversion to ammonia of 16.25μg·h^(-1)·mg_(cat.)^(-1)at the potential of-0.3 V relative to the reversible hydrogen electrode(RHE)with a Faraday efficiency of 20.51%.The electrocatalyst showed good stability even after 12 times recyclability under environmental conditions and neutral electrolyte.Later,the electrocatalytic nitrogen reduction performance of CaFeO_(x),CaNiO_(x),CaCuO_(x)was investigated.These earth-rich transition metals also exhibited certain NRR electrocatalytic capabilities,which provided a door for further development of inexpensive and easily available transition metal as nitrogen reduction electrocatalysts.展开更多
Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to...Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to improve the capacitance and energy density of solid-state supercapacitors(SCs).In this study,polyoxometalates(POMs)are applied as proton conductors and redox mediators in polyvinyl alcohol(PVA)electrolytes,which increase the capacitance of obtained SCs with polyaniline(PANI).H_(3)PMo_(12)O_(40)-loaded PANI electrodes provide pseudocapacitance with an eight-electron Faraday reaction in a charge–discharge cycle.This has rarely been reported in SCs before.The largest capacitance of SCs with H_(3)PMo_(12)O_(40)and H_(3)PW_(12)O_(40)as electrolytes is 7.69 F/cm^(2)(3840 F/g)based on a single electrode at 0.5 mA/cm^(2).In addition,POM electrolytes exhibit excellent self-healing ability,which is attributed to the rich hydrogen-bonding network between POMs and PVA.This study demonstrates that the capacitance of solid-state SCs is improved by using molecular redox-active electrolytes and showcases the potential of applying this strategy to other energy storage devices in the future.展开更多
基金financial support from the National Natural Science Foundation of China(No.21871042,21471028,No.21671036,No.21673098,No.21975211)support from the Innovative Research Group Project of NSFC(22021001)+5 种基金the National Key Research and Development Program(2021YFA1502300)Changbai Mountain Scholarship,Natural Science Foundation of Jilin Province(No.20200201083JC)Natural Science Foundation of Department of Education of Jilin Province(No.JJKH20201169KJ)the Fundamental Research Funds for the Central Universities(20720190035)Nanqiang Young Top-notch Talent Fellowship in Xiamen Universitysupported by Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences.
文摘Solid-state electrolytes have attracted considerable attention in new energyrelated devices due to their high safety and broad application platform.Polyoxometalates(POMs)are a kind of molecular-level cluster compounds with unique structures.In recent years,owing to their abundant physicochemical properties(including high ionic conductivity and reversible redox activity),POMs have shown great potential in becoming a new generation of solid-state electrolytes.In this review,an overview is investigated about how POMs have evolved as ion-conducting materials from basic research to novel solid-state electrolytes in energy devices.First,some expressive POM-based ion-conducting materials in recent years are introduced and classified,mainly inspecting their structural and functional relationship.After that,it is further focused on the application of these ionconducting electrolytes in the fields of proton exchange membranes,supercapacitors,and ion batteries.In addition,some properties of POMs(such as inherent dimension,capable of forming stable hydrogen bonds,and reversible bonding to water molecules)enable these functional POM-based electrolytes to be employed in innovative applications such as ion selection,humidity sensing,and smart materials.Finally,some fundamental recommendations are given on the current opportunities and challenges of POM-based ion-conducting electrolytes.
基金the financial support from the National Natural Science Foundation of China(Nos.21871042,21471028,21671036),Changbai Mountain Scholarship,N atural Science Foundation of Jilin Province(No.20200201083JC)Natural Science Foundation of Department of education of Jilin Province(No.JJKH20201169KJ).
文摘In order to sustainably transform N2 to ammonia(NRR)using electrocatalysts under mild ambient condition,it is urgent to design and develop non-nobel metal nanocatalysts that are inexpensive and suitable for mass-production.Herein,a calcium metalate catalyst CaCoO_(x)with oxygen vacancies was synthesized and used as an electrocatalyst for NRR for the first time,whose morphology can be controlled by the calcination temperature and the heating rate.Under the optimal conditions,the CaCoO_(x)catalyst achieved the yield of nitrogen conversion to ammonia of 16.25μg·h^(-1)·mg_(cat.)^(-1)at the potential of-0.3 V relative to the reversible hydrogen electrode(RHE)with a Faraday efficiency of 20.51%.The electrocatalyst showed good stability even after 12 times recyclability under environmental conditions and neutral electrolyte.Later,the electrocatalytic nitrogen reduction performance of CaFeO_(x),CaNiO_(x),CaCuO_(x)was investigated.These earth-rich transition metals also exhibited certain NRR electrocatalytic capabilities,which provided a door for further development of inexpensive and easily available transition metal as nitrogen reduction electrocatalysts.
基金support from the National Natural Science Foundation of China(nos.21871042,21471028,and 21673098)。
文摘Energy storage devices with high volumetric and gravimetric capacitance are in urgent demand due to the booming market of portable and wearable electronics.Using redox-active molecules as electrolytes is a strategy to improve the capacitance and energy density of solid-state supercapacitors(SCs).In this study,polyoxometalates(POMs)are applied as proton conductors and redox mediators in polyvinyl alcohol(PVA)electrolytes,which increase the capacitance of obtained SCs with polyaniline(PANI).H_(3)PMo_(12)O_(40)-loaded PANI electrodes provide pseudocapacitance with an eight-electron Faraday reaction in a charge–discharge cycle.This has rarely been reported in SCs before.The largest capacitance of SCs with H_(3)PMo_(12)O_(40)and H_(3)PW_(12)O_(40)as electrolytes is 7.69 F/cm^(2)(3840 F/g)based on a single electrode at 0.5 mA/cm^(2).In addition,POM electrolytes exhibit excellent self-healing ability,which is attributed to the rich hydrogen-bonding network between POMs and PVA.This study demonstrates that the capacitance of solid-state SCs is improved by using molecular redox-active electrolytes and showcases the potential of applying this strategy to other energy storage devices in the future.