Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage,yet suffer from poor intrinsic ionic conductivity and(el...Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage,yet suffer from poor intrinsic ionic conductivity and(electro)chemical instability at high temperatures.Herein,a cation-modified Na_(2.466)Fe_(1.724)Mg_(0.043)(SO_(4))_(3)with micron-sized spherical structure was reported.The substitutive MgO_(6)octahedron featured stronger covalent bonding interactions and enriched the ion transfer pathways within the crystals,facilitating the ionic kinetics in bulk.Using in situ mass spectrometry and quartz crystal microbalance techniques,Mg cations were demonstrated to lower the electron density around O atoms and surficial nucleophilicity of materials,which effectively suppressed their side reactions with H_(2)O in air and active ester molecule in electrolyte.This interaction enables an inorganic-rich and uniform interphase to stabilize the cathode/electrolyte interface at high voltage(4.5 V vs.Na^(+)/Na).The as-prepared cathode exhibits a high discharge capacity of 102.2 mAh g^(-1)(voltage platform at 3.74 V),remarkable reaction reversibility(average Coulomb efficiency of 99.3%over 300 cycles)at high loading(9.0-9.6 mg cm^(-2))and temperature(60℃),as well as long-lasting cyclability(70.8%,5000 cycles).Its application was verified in assembled sodium-ion full cells with a hard carbon negative electrode,showing a long cycling lifetime over 190 cycles.展开更多
Benefiting from the environmental friendliness of organic electrodes and the high security of aqueous electrolyte,an all-organic aqueous potassium dual-ion full battery(APDIB) was assembled with 21 M potassium bis(flu...Benefiting from the environmental friendliness of organic electrodes and the high security of aqueous electrolyte,an all-organic aqueous potassium dual-ion full battery(APDIB) was assembled with 21 M potassium bis(fluoroslufonyl)imide(KFSI) water-in-salt as the electrolyte.The APDIB could deliver a reversible capacity of around 50 mAh g^(-1) at 200 mA g^(-1)(based on the weight of total active materials),a long cycle stability over 900 cycles at 500 mA g^(-1) and a high coulombic efficiency of 98.5%.The reaction mechanism of APDIB during the charge/discharge processes is verified:the FSI-could associate/disassociate with the nitrogen atom in the polytriphenylamine(PTPAn) cathode,while the K^(+) could react with C=O bonds in the 3,4,9,10-perylenetetracarboxylic diimide(PTCDI) anode reversibly.Our work contributes toward the understanding the nature of water-into-salt electrolyte and successfully constructed all-organic APDIB.展开更多
Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cyclin...Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cycling stability.Herein,we reported a metal-organic coordination interface(2-mercaptobenzothiazole-Cu)on the HC anode and particles(HC@MBT-Cu)to obtain the desired solid electrolyte interphase(SEI)and reduce the polarization of plateau-region sodium storage for durable SIBs.In the metal-organic coordination interface,Cu cations as catalytic centers coordinated with PF6-for easier breakage of P-F bonds to form CuF_(2)and NaF into SEI.Cu and Na cations coordinate with exocyclic S groups of the decoration interface,promoting the breakage of C-S bonds and obtaining Na2S and CuS in SEI.Meanwhile,N,S rigid-ring groups contribute to the SEI's elasticity.Ultimately,thin elastic(Cu-F/S,Na-F/S)-rich SEI(14-18 nm,Cryo-TEM)was constructed with less electrolyte consumption and significantly reduced gas production.As a result,the polarization voltage of HC greatly decreased.The assembled HC@MBT-Cu||Na_(3)V_(2)(PO_(4))_(3)full cells exhibited 86.4%after 600 cycles and pouch cells had a high-energy density of 175.1 Wh kg^(-1).This work not only provides new insight into interface engineering but also offers a strategy to enhance the stability of HC particles and anodes,which might promote the development process of SIBs.展开更多
Sodium metal batteries are emerging as promising energy storage technologies owing to their high-energy density and rich resources.However,the challenge of achieving continuous operation at high areal capacity hinders...Sodium metal batteries are emerging as promising energy storage technologies owing to their high-energy density and rich resources.However,the challenge of achieving continuous operation at high areal capacity hinders the application of this system.Here,a robust two-dimensional tin/sodium‒tin alloy interface was introduced onto an Al substrate as an anode via an industrial electroplating strategy.Unlike the widely accepted in situ formation of Na15Sn4 alloys,the formation of Na_(9)Sn_(4)alloys results in a semi-coherent interface with sodium due to low lattice mismatch(20.84%),which alleviates the lattice stress of sodium deposition and induces subsequent dense sodium deposition under high areal capacity.In addition,the strong interaction of Sn with anions allows more PF6−to preferentially participate in the interfacial solvation structure,thereby facilitating the formation of a thin(10 nm)NaF-rich solid electrolyte interface.Therefore,the substrate can withstand a high areal capacity of 5 mA h cm^(-2),exhibiting a high average Coulombic efficiency of 99.7%.The full battery exhibits long-term cycling performance(600 cycles)with a low decay rate of 0.0018%per cycle at 60 mA g^(-1).展开更多
As the key to optimizing potassium ion batteries’(PIBs)performance,the development of high capacity potassium anode is the footstone.Here,through a one-step solvothermal method,uniformly dispersed SbVO4 nanoparticles...As the key to optimizing potassium ion batteries’(PIBs)performance,the development of high capacity potassium anode is the footstone.Here,through a one-step solvothermal method,uniformly dispersed SbVO4 nanoparticles on the reduced graphene oxide nanosheets(SbVO4@RGO)were synthesized and used as PIBs anodes.SbVO4@RGO anode shows high capacity due to alloying and conversion reactions occur simultaneously in the cyclic process.The anode delivers a capacity as high as 447.9 mAh g^-1 at 100 mA g^-1.Besides,a cycling life of 500 cycles with small average capacity decay rate(only 0.106%per cycle)is also revealed.It was found in the initial discharge process,SbVO4 transforms into Sb and K3VO4.And in the following cycle Sb and K3VO4 simultaneously react with K+via the alloying/de-alloying and conversion reaction,respectively.The present study of SbVO4@RGO may provide insight for high performance alloying-based/conversion-based potassium anodes.展开更多
The urgent need for highly safe and sustainable large-scale energy storage systems for residential buildings has led to research into aqueous zinc ion batteries.However,when zinc is used in aqueous zinc ion batteries,...The urgent need for highly safe and sustainable large-scale energy storage systems for residential buildings has led to research into aqueous zinc ion batteries.However,when zinc is used in aqueous zinc ion batteries,it suffers from severe irreversibility due to its low Coulombic efficiency,dendrite growth,and side reactions.To address these challenges,we take advantage of organic cation to induce trifluoromethanesulfonate decomposition to build zinc fluoride/zinc sulfide-rich solid electrolyte interphase(SEI)that not only can adapt to a high areal capacity of deposition/stripping disturbance but also adjust zinc ion deposition path to eliminate dendrite.As a result,the unique interface can promote the Zn battery to achieve excellent electrochemical performance:high levels of plating/stripping Coulombic efficiency(99.8%),stability life(6,600 h),and cumulative capacity(66,000 mAh·cm^(−2))at 68%zinc utilization(20 mAh·cm^(−2)).More importantly,the SEI significantly enhances the cyclability of full battery under limited Zn,lean electrolyte,and high areal capacity cathode conditions.展开更多
基金support from the Joint Fund of Scientific and Technological Research and Development Program of Henan Province(222301420009)National Natural Science Foundation of China(22279121,22409179)+1 种基金Key Research and Development Program of Henan Province(231111241400)Longzihu new energy laboratory project(LZHLH202300)and the funding of Zhengzhou University.
文摘Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage,yet suffer from poor intrinsic ionic conductivity and(electro)chemical instability at high temperatures.Herein,a cation-modified Na_(2.466)Fe_(1.724)Mg_(0.043)(SO_(4))_(3)with micron-sized spherical structure was reported.The substitutive MgO_(6)octahedron featured stronger covalent bonding interactions and enriched the ion transfer pathways within the crystals,facilitating the ionic kinetics in bulk.Using in situ mass spectrometry and quartz crystal microbalance techniques,Mg cations were demonstrated to lower the electron density around O atoms and surficial nucleophilicity of materials,which effectively suppressed their side reactions with H_(2)O in air and active ester molecule in electrolyte.This interaction enables an inorganic-rich and uniform interphase to stabilize the cathode/electrolyte interface at high voltage(4.5 V vs.Na^(+)/Na).The as-prepared cathode exhibits a high discharge capacity of 102.2 mAh g^(-1)(voltage platform at 3.74 V),remarkable reaction reversibility(average Coulomb efficiency of 99.3%over 300 cycles)at high loading(9.0-9.6 mg cm^(-2))and temperature(60℃),as well as long-lasting cyclability(70.8%,5000 cycles).Its application was verified in assembled sodium-ion full cells with a hard carbon negative electrode,showing a long cycling lifetime over 190 cycles.
基金financially supported by the National Natural Science Foundation of China (Nos.51922038 and 51672078)the Hunan Outstanding Youth Talents(No.2019JJ20005)+1 种基金Hunan Provincial Natural Science Foundation of China(2019JJ40031)the Fundamental Research Funds for the Central Universities(531119200156)。
文摘Benefiting from the environmental friendliness of organic electrodes and the high security of aqueous electrolyte,an all-organic aqueous potassium dual-ion full battery(APDIB) was assembled with 21 M potassium bis(fluoroslufonyl)imide(KFSI) water-in-salt as the electrolyte.The APDIB could deliver a reversible capacity of around 50 mAh g^(-1) at 200 mA g^(-1)(based on the weight of total active materials),a long cycle stability over 900 cycles at 500 mA g^(-1) and a high coulombic efficiency of 98.5%.The reaction mechanism of APDIB during the charge/discharge processes is verified:the FSI-could associate/disassociate with the nitrogen atom in the polytriphenylamine(PTPAn) cathode,while the K^(+) could react with C=O bonds in the 3,4,9,10-perylenetetracarboxylic diimide(PTCDI) anode reversibly.Our work contributes toward the understanding the nature of water-into-salt electrolyte and successfully constructed all-organic APDIB.
基金supported by the National Natural Science Foundation of China(22279121,U24A200471,22209153)the Key Research and Development Program of Henan Province(231111241400)+3 种基金the Joint Fund of Scientific and Technological Research and Development Program of Henan Province(222301420009)Zhengzhou Universitysupported by the National Supercomputing Centre in Zhengzhouthe funding of Zhengzhou University。
文摘Large-scale applications of resource-enriched sodium-ion batteries(SIBs)suffer serious obstacles on the hard carbon(HC)anode due to large interface resistance and continuous electrolyte consumption induced poor cycling stability.Herein,we reported a metal-organic coordination interface(2-mercaptobenzothiazole-Cu)on the HC anode and particles(HC@MBT-Cu)to obtain the desired solid electrolyte interphase(SEI)and reduce the polarization of plateau-region sodium storage for durable SIBs.In the metal-organic coordination interface,Cu cations as catalytic centers coordinated with PF6-for easier breakage of P-F bonds to form CuF_(2)and NaF into SEI.Cu and Na cations coordinate with exocyclic S groups of the decoration interface,promoting the breakage of C-S bonds and obtaining Na2S and CuS in SEI.Meanwhile,N,S rigid-ring groups contribute to the SEI's elasticity.Ultimately,thin elastic(Cu-F/S,Na-F/S)-rich SEI(14-18 nm,Cryo-TEM)was constructed with less electrolyte consumption and significantly reduced gas production.As a result,the polarization voltage of HC greatly decreased.The assembled HC@MBT-Cu||Na_(3)V_(2)(PO_(4))_(3)full cells exhibited 86.4%after 600 cycles and pouch cells had a high-energy density of 175.1 Wh kg^(-1).This work not only provides new insight into interface engineering but also offers a strategy to enhance the stability of HC particles and anodes,which might promote the development process of SIBs.
基金supported by the Science Technology and Innovation Team in the Universities of Henan Province(24IRTSTHN002)the National Natural Science Foundation of China(22279121and 22409179)+1 种基金supported by the National Supercomputing Centre in Zhengzhouthe funding of Zhengzhou University。
文摘Sodium metal batteries are emerging as promising energy storage technologies owing to their high-energy density and rich resources.However,the challenge of achieving continuous operation at high areal capacity hinders the application of this system.Here,a robust two-dimensional tin/sodium‒tin alloy interface was introduced onto an Al substrate as an anode via an industrial electroplating strategy.Unlike the widely accepted in situ formation of Na15Sn4 alloys,the formation of Na_(9)Sn_(4)alloys results in a semi-coherent interface with sodium due to low lattice mismatch(20.84%),which alleviates the lattice stress of sodium deposition and induces subsequent dense sodium deposition under high areal capacity.In addition,the strong interaction of Sn with anions allows more PF6−to preferentially participate in the interfacial solvation structure,thereby facilitating the formation of a thin(10 nm)NaF-rich solid electrolyte interface.Therefore,the substrate can withstand a high areal capacity of 5 mA h cm^(-2),exhibiting a high average Coulombic efficiency of 99.7%.The full battery exhibits long-term cycling performance(600 cycles)with a low decay rate of 0.0018%per cycle at 60 mA g^(-1).
基金the National Natural Science Foundation of China(51922038,51672078)Hunan Outstanding Youth Talents(2019JJ20005),Hunan Provincial Natural Science Foundation of China(2019JJ40031)Fundamental Research Funds for the Central Universities。
文摘As the key to optimizing potassium ion batteries’(PIBs)performance,the development of high capacity potassium anode is the footstone.Here,through a one-step solvothermal method,uniformly dispersed SbVO4 nanoparticles on the reduced graphene oxide nanosheets(SbVO4@RGO)were synthesized and used as PIBs anodes.SbVO4@RGO anode shows high capacity due to alloying and conversion reactions occur simultaneously in the cyclic process.The anode delivers a capacity as high as 447.9 mAh g^-1 at 100 mA g^-1.Besides,a cycling life of 500 cycles with small average capacity decay rate(only 0.106%per cycle)is also revealed.It was found in the initial discharge process,SbVO4 transforms into Sb and K3VO4.And in the following cycle Sb and K3VO4 simultaneously react with K+via the alloying/de-alloying and conversion reaction,respectively.The present study of SbVO4@RGO may provide insight for high performance alloying-based/conversion-based potassium anodes.
基金supported by the National Natural Science Foundation of China(No.22279121)Joint Fund of Scientific and Technological Research and Development Program of Henan Province(No.222301420009).
文摘The urgent need for highly safe and sustainable large-scale energy storage systems for residential buildings has led to research into aqueous zinc ion batteries.However,when zinc is used in aqueous zinc ion batteries,it suffers from severe irreversibility due to its low Coulombic efficiency,dendrite growth,and side reactions.To address these challenges,we take advantage of organic cation to induce trifluoromethanesulfonate decomposition to build zinc fluoride/zinc sulfide-rich solid electrolyte interphase(SEI)that not only can adapt to a high areal capacity of deposition/stripping disturbance but also adjust zinc ion deposition path to eliminate dendrite.As a result,the unique interface can promote the Zn battery to achieve excellent electrochemical performance:high levels of plating/stripping Coulombic efficiency(99.8%),stability life(6,600 h),and cumulative capacity(66,000 mAh·cm^(−2))at 68%zinc utilization(20 mAh·cm^(−2)).More importantly,the SEI significantly enhances the cyclability of full battery under limited Zn,lean electrolyte,and high areal capacity cathode conditions.
