Rechargeable lithium-carbon dioxide(Li-CO_(2))batteries have emerged as a highly promising approach to simultaneously address energy shortages and the greenhouse effect.However,certain limitations exist in Li-CO_(2)ba...Rechargeable lithium-carbon dioxide(Li-CO_(2))batteries have emerged as a highly promising approach to simultaneously address energy shortages and the greenhouse effect.However,certain limitations exist in Li-CO_(2)batteries like high charge overpotential and unstable Li metal interface,which adversely affect the energy efficiency and cycling life.The incorporation of soluble redox mediators(RMs)has proven effective in enhancing the charge transfer between lithium carbonate(Li_(2)CO_(3))and cathode,thereby substantially reducing the charge overpotential.Nevertheless,the severe shuttle effect of RMs results in the reactions with Li anode,not only exacerbating the corrosion of Li anode but also leading to the depletion of RMs and electrical energy efficiency.In this work,an organic compound containing large cation group,1-ethyl-3-methylimidazole bromide(EMIBr)is proposed as the defense donor RM for Li anode in Li-CO_(2)batteries to address the above problems simultaneously.During charging,Li_(2)CO_(3)oxidation kinetics can be accelerated by bromide anion pair(Br_(3)^(−)/Br^(−)).Meanwhile,the cations(EMI^(+))are preferentially adsorbed around the protruding tips of Li anode through electrostatic interaction driven by surface free energy,forming protective layers that effectively inhibit further Li deposition at these tips,which is verified by DFT calculations.Additionally,Li dendrites growth is inhibited by the electrostatic repulsion of polar groups in EMIBr,resulting in uniform Li deposition.Consequently,a lower overpotential(∼1.17 V)and a longer cycle life(∼200 cycles)have been obtained for Li-CO_(2)battery incorporating EMIBr.展开更多
The coupling of fast redox kinetics,high-energy density,and prolonged lifespan is a permanent aspiration for aqueous rechargeable zinc batteries,but which has been severely hampered by a narrow voltage range and subop...The coupling of fast redox kinetics,high-energy density,and prolonged lifespan is a permanent aspiration for aqueous rechargeable zinc batteries,but which has been severely hampered by a narrow voltage range and suboptimal compatibility between the electrolytes and electrodes.Here,we unprecedentedly introduced an electric ambipolar effect for synergistic manipulation on Zn^(2+)ternary-hydrated eutectic electrolyte(ZTE)enabling high-performance Zn-Br_(2)batteries.The electric ambipolar effect motivates strong dipole interactions among hydrated perchlorates and bipolar ligands of L-carnitine(L-CN)and sulfamide,which reorganized primary cations solvation sheath in a manner of forming Zn[(L-CN)(SA)(H_(2)O)_(4)]^(2+)configuration and dynamically restricting desolvated H2O molecules,thus ensuring a broadened electrochemical window of 2.9 V coupled with high ionic conductivity.Noticeably,L-CN affords an electrostatic shielding effect and an in situ construction of organic-inorganic interphase,endowing oriented Zn anode plating/stripping reversibly for over 2400 h.Therefore,with the synergy of electro/nucleophilicity and exceptional compatibility,the ZTE electrolyte dynamically boosts the conversion redox of Zn-Br_(2)batteries in terms of high specific capacity and stable cycling performance.These findings open a window for designing electrolytes with synergetic chemical stability and compatibility toward advanced zinc-ion batteries.展开更多
Graphene oxide(GO),an important chemical precursor of graphene,can stably disperse in aqueous surrounding and undergo aggregation as metal cations introduced.The usual instability of GO with ions is caused by the shie...Graphene oxide(GO),an important chemical precursor of graphene,can stably disperse in aqueous surrounding and undergo aggregation as metal cations introduced.The usual instability of GO with ions is caused by the shielding effect of ions and crosslinking between GO and ions.However,the dynamic stability of GO under ions exchange still remains unclear.Here,we investigated the dynamic dispersion stability of GO with metal ions and observed a redispersion behavior in concentrated Fe3+solution,other than permanent aggregation.The exchange with Fe3+ions drives the reversion of zeta(ζ)potential and enables the redispersion to individual GO-Fe3+complex sheets,following a dynamic electric double layer(EDL)mechanism.It is found that the specifically strong electrostatic shielding effect and coordination attraction between Fe3+and functional oxygen groups allows the selective redispersion of GO in concentrated Fe3+solution.The revealed dynamic dispersion stability complements our understanding on the dispersive stability of GO and can be utilized to fabricate graphene-metal hybrids for rich applications.展开更多
Metallic zinc is an excellent anode material for Zn-ion batteries,but the growth of Zn dendrite severely hinders its practical application.Herein,an efficient and economical cationic additive,poly dimethyl diallyl amm...Metallic zinc is an excellent anode material for Zn-ion batteries,but the growth of Zn dendrite severely hinders its practical application.Herein,an efficient and economical cationic additive,poly dimethyl diallyl ammonium(PDDA) was reported,used in aqueous Zn-ion batteries electrolyte for stabilizing Zn anode.The growth of zinc dendrites can be significantly restrained by benefiting from the pronounced electrostatic shielding effect from PDDA on the Zn metal surface.Moreover,the PDDA is preferentially absorbed on Zn(002) plane,thus preventing unwanted side reactions on Zn anode.Owing to the introduction of a certain amount of PDDA additive into the common ZnSO_(4)-based electrolyte,the cycle life of assembled Zn‖Zn cells(1 mA·cm^(-2) and 1 mAh·cm^(-2)) is prolonged to more than 1100 h.In response to the perforation issue of Zn electrodes caused by PDDA additives,the problem can be solved by combining foamy copper with zinc foil.For real application,Zn-ion hybrid supercapacitors and MnO_(2)‖Zn cells were assembled,which exhibited excellent cycling stability with PDDA additives.This work provides a new solution and perspective to cope with the dendrite growth problem of Zn anode.展开更多
A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle ...A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle life.The mechanism behind the enhanced electrochemical performance of the“salt-in-metal”composite is investigated,where KNO_(3) in metallic Li composite electrode would be sustainably released into the electrolyte.The presence of NO_(3)-stabilizes the solid electrolyte interphase by producing functional Li_(3)N,LiNxOy,and Li_(2)O species.K^(+)from KNO_(3) also helps to form an electrostatic shield after its adsorption on the electrode protrusions,which suppresses the dendritic growth of metallic Li.With the above advantages,uniform Li plating with dense and planar structure is realized for the LKNO electrode.These findings reveal a deep understanding of the effect of the“saltin-metal”anode and provide new insights into the use of nitrate additives for high-energy-density Li metal batteries.展开更多
Lithium–sulfur(Li-S) battery is considered as one of the most promising candidates for future portable electronics and electric vehicles due to high energy density and potentially low cost. However, the severe polysu...Lithium–sulfur(Li-S) battery is considered as one of the most promising candidates for future portable electronics and electric vehicles due to high energy density and potentially low cost. However, the severe polysulfides shuttling in Li-S battery always causes low Coulombic efficiency, capacity fading, and hindering its practical commercialization. Herein, a dualfunctional PEI@MWCNTs-CB/MWCNTs/PP(briefly denoted as PMS)separator is assembled through Langmuir–Blodgett–Scooping(LBS) technique for improvement of Li-S battery performance, that is, rational integrating conductive MWCNTs multilayer on a routine PP separator with polyethyleneimine(PEI) polymer. Owing to "proton-sponge"-based PEI feature with the abundant amino/imine groups and branched structures, the PMS separator can provide strong affinity to immobilize the negatively charged polysulfides via electrostatic interaction. Simultaneously,incorporated with the conductive MWCNTs multilayers for the electron transportation, the Li-S cells assembled with PMS separators achieve exceptional high delivery capacity, good rate performance(~550 m Ah g-1 at a current density of 9 A g-1), and stable cycling retention(retention of84.5% at a current density of 1 A g-1) even over 120 cycles, especially in the case of high-loading sulfur cathode(80 wt% of S content). This multifunctional separator with dual-structural architectures via self-assembly LBS method paves new avenues to develop high-performance Li-S batteries.展开更多
基金financially supported by National Natural Science Foundation of China(No.22075171).
文摘Rechargeable lithium-carbon dioxide(Li-CO_(2))batteries have emerged as a highly promising approach to simultaneously address energy shortages and the greenhouse effect.However,certain limitations exist in Li-CO_(2)batteries like high charge overpotential and unstable Li metal interface,which adversely affect the energy efficiency and cycling life.The incorporation of soluble redox mediators(RMs)has proven effective in enhancing the charge transfer between lithium carbonate(Li_(2)CO_(3))and cathode,thereby substantially reducing the charge overpotential.Nevertheless,the severe shuttle effect of RMs results in the reactions with Li anode,not only exacerbating the corrosion of Li anode but also leading to the depletion of RMs and electrical energy efficiency.In this work,an organic compound containing large cation group,1-ethyl-3-methylimidazole bromide(EMIBr)is proposed as the defense donor RM for Li anode in Li-CO_(2)batteries to address the above problems simultaneously.During charging,Li_(2)CO_(3)oxidation kinetics can be accelerated by bromide anion pair(Br_(3)^(−)/Br^(−)).Meanwhile,the cations(EMI^(+))are preferentially adsorbed around the protruding tips of Li anode through electrostatic interaction driven by surface free energy,forming protective layers that effectively inhibit further Li deposition at these tips,which is verified by DFT calculations.Additionally,Li dendrites growth is inhibited by the electrostatic repulsion of polar groups in EMIBr,resulting in uniform Li deposition.Consequently,a lower overpotential(∼1.17 V)and a longer cycle life(∼200 cycles)have been obtained for Li-CO_(2)battery incorporating EMIBr.
基金provided by the National Natural Science Foundation of China(Grant No.52373208 and 61831021)the ECNU Academic Innovation Promotion Program for Excellent Doctoral Students(YBNLTS2024-021).
文摘The coupling of fast redox kinetics,high-energy density,and prolonged lifespan is a permanent aspiration for aqueous rechargeable zinc batteries,but which has been severely hampered by a narrow voltage range and suboptimal compatibility between the electrolytes and electrodes.Here,we unprecedentedly introduced an electric ambipolar effect for synergistic manipulation on Zn^(2+)ternary-hydrated eutectic electrolyte(ZTE)enabling high-performance Zn-Br_(2)batteries.The electric ambipolar effect motivates strong dipole interactions among hydrated perchlorates and bipolar ligands of L-carnitine(L-CN)and sulfamide,which reorganized primary cations solvation sheath in a manner of forming Zn[(L-CN)(SA)(H_(2)O)_(4)]^(2+)configuration and dynamically restricting desolvated H2O molecules,thus ensuring a broadened electrochemical window of 2.9 V coupled with high ionic conductivity.Noticeably,L-CN affords an electrostatic shielding effect and an in situ construction of organic-inorganic interphase,endowing oriented Zn anode plating/stripping reversibly for over 2400 h.Therefore,with the synergy of electro/nucleophilicity and exceptional compatibility,the ZTE electrolyte dynamically boosts the conversion redox of Zn-Br_(2)batteries in terms of high specific capacity and stable cycling performance.These findings open a window for designing electrolytes with synergetic chemical stability and compatibility toward advanced zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(Nos.51533008,51603183,51703194,51803177,21805242 and 5197030056)National Key R&D Program of China(No.2016YFA0200200)+4 种基金Fujian Provincial Science and Technology Major Projects(No.2018HZ0001-2)Hundred Talents Program of Zhejiang University(No.188020*194231701/113)Key Research and Development Plan of Zhejiang Province(No.2018C01049)the Fundamental Research Funds for the Central Universities(Nos.2017QNA4036,2017XZZX001-04)Foundation of National Key Laboratory on Electromagnetic Environment Effects(No.614220504030717)。
文摘Graphene oxide(GO),an important chemical precursor of graphene,can stably disperse in aqueous surrounding and undergo aggregation as metal cations introduced.The usual instability of GO with ions is caused by the shielding effect of ions and crosslinking between GO and ions.However,the dynamic stability of GO under ions exchange still remains unclear.Here,we investigated the dynamic dispersion stability of GO with metal ions and observed a redispersion behavior in concentrated Fe3+solution,other than permanent aggregation.The exchange with Fe3+ions drives the reversion of zeta(ζ)potential and enables the redispersion to individual GO-Fe3+complex sheets,following a dynamic electric double layer(EDL)mechanism.It is found that the specifically strong electrostatic shielding effect and coordination attraction between Fe3+and functional oxygen groups allows the selective redispersion of GO in concentrated Fe3+solution.The revealed dynamic dispersion stability complements our understanding on the dispersive stability of GO and can be utilized to fabricate graphene-metal hybrids for rich applications.
基金financially supported by Fuzhou science and technology project (Nos.2021-ZD-213 and 2020-Z-6)Fujian Provincial Department of Science and Technology(Nos.2021T3036,2020T3004,2020T3030 and 2020H0040)+2 种基金STS Science And Technology Project of the Chinese Academy of Sciences(No.KFJ-STS-QYZD-2021-09-001)Quanzhou Science and Technology Project (No.2020G17)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (No.2021009)。
文摘Metallic zinc is an excellent anode material for Zn-ion batteries,but the growth of Zn dendrite severely hinders its practical application.Herein,an efficient and economical cationic additive,poly dimethyl diallyl ammonium(PDDA) was reported,used in aqueous Zn-ion batteries electrolyte for stabilizing Zn anode.The growth of zinc dendrites can be significantly restrained by benefiting from the pronounced electrostatic shielding effect from PDDA on the Zn metal surface.Moreover,the PDDA is preferentially absorbed on Zn(002) plane,thus preventing unwanted side reactions on Zn anode.Owing to the introduction of a certain amount of PDDA additive into the common ZnSO_(4)-based electrolyte,the cycle life of assembled Zn‖Zn cells(1 mA·cm^(-2) and 1 mAh·cm^(-2)) is prolonged to more than 1100 h.In response to the perforation issue of Zn electrodes caused by PDDA additives,the problem can be solved by combining foamy copper with zinc foil.For real application,Zn-ion hybrid supercapacitors and MnO_(2)‖Zn cells were assembled,which exhibited excellent cycling stability with PDDA additives.This work provides a new solution and perspective to cope with the dendrite growth problem of Zn anode.
基金Y.Sun acknowledges the financial support of the National Natural Science Foundation of China(No.52072137)Z.W.Seh acknowledges the support of the Singapore National Research Foundation(NRF-NRFF2017-04).
文摘A Li/KNO_(3) composite(LKNO),with KNO_(3) uniformly implanted in bulk metallic Li,is fabricated for battery anode via a facile mechanical kneading approach,which exhibits high Coulombic efficiency and prolonged cycle life.The mechanism behind the enhanced electrochemical performance of the“salt-in-metal”composite is investigated,where KNO_(3) in metallic Li composite electrode would be sustainably released into the electrolyte.The presence of NO_(3)-stabilizes the solid electrolyte interphase by producing functional Li_(3)N,LiNxOy,and Li_(2)O species.K^(+)from KNO_(3) also helps to form an electrostatic shield after its adsorption on the electrode protrusions,which suppresses the dendritic growth of metallic Li.With the above advantages,uniform Li plating with dense and planar structure is realized for the LKNO electrode.These findings reveal a deep understanding of the effect of the“saltin-metal”anode and provide new insights into the use of nitrate additives for high-energy-density Li metal batteries.
基金support of the National Natural Science Foundation of China (51671135, 21875141)support of the Program of Shanghai Subject Chief Scientist (17XD1403000)+2 种基金Innovation Program of Shanghai Municipal Education Commission (2019-01-07-00-07-E00015)Shanghai Outstanding Academic Leaders Plan, Shanghai Pujiang Program (18PJ1409000)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources (SKL-ACPS-C-23)
文摘Lithium–sulfur(Li-S) battery is considered as one of the most promising candidates for future portable electronics and electric vehicles due to high energy density and potentially low cost. However, the severe polysulfides shuttling in Li-S battery always causes low Coulombic efficiency, capacity fading, and hindering its practical commercialization. Herein, a dualfunctional PEI@MWCNTs-CB/MWCNTs/PP(briefly denoted as PMS)separator is assembled through Langmuir–Blodgett–Scooping(LBS) technique for improvement of Li-S battery performance, that is, rational integrating conductive MWCNTs multilayer on a routine PP separator with polyethyleneimine(PEI) polymer. Owing to "proton-sponge"-based PEI feature with the abundant amino/imine groups and branched structures, the PMS separator can provide strong affinity to immobilize the negatively charged polysulfides via electrostatic interaction. Simultaneously,incorporated with the conductive MWCNTs multilayers for the electron transportation, the Li-S cells assembled with PMS separators achieve exceptional high delivery capacity, good rate performance(~550 m Ah g-1 at a current density of 9 A g-1), and stable cycling retention(retention of84.5% at a current density of 1 A g-1) even over 120 cycles, especially in the case of high-loading sulfur cathode(80 wt% of S content). This multifunctional separator with dual-structural architectures via self-assembly LBS method paves new avenues to develop high-performance Li-S batteries.
