The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Althoug...The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Although cosolvent engineering has shown promise in mitigating water activity through hydrogenbond network modulation,prevailing strategies remain limited by their narrow focus on electronic and functional group properties,neglecting the stereochemical influence on molecular assembly.In this work,we uncover how molecular chirality dictates the hierarchical organization of hydrogen-bonding networks between cosolvents and water,which is a critical but previously unrecognized determinant of interfacial stability.By interrogating enantiomeric pairs(L-/D-carnitine),we demonstrate that chiral constraints steer the spatial arrangement of hydration structures through stereoselective hydrogenbonding geometries.Combined spectroscopic and molecular dynamics analyses reveal that L-carnitine(L-CN)forms a three-dimensional hydrogen-bonded matrix with water,exhibiting superior directional connectivity relative to its D-isomer.This stereo-dependent architecture simultaneously reinforces Zn2+solvation shells via bridging H-bond interactions and generates a self-adaptive interfacial structure that kinetically isolates water from the zinc anode surface.This stereochemical optimization enables Zn||Zn symmetric cells with unprecedented cycling stability exceeding 2000 h at 0.5 mA cm^(-2)/0.5 mAh cm^(-2).Corresponding Zn||Cu asymmetric cells maintain a high average Coulombic efficiency of 99.7%over 500 cycles at 3.0 mA cm^(-2)/3.0 mAh cm^(-2).This study pioneers a stereochemical design framework for aqueous electrolytes,elucidating chiral recognition mechanisms in solvation structures and establishing molecular topology engineering as a transformative strategy for high-efficiency energy storage systems.展开更多
Copper is difficult to separate from nickel electrolyte due to low concentration of copper (0.53 g/L) with high concentration of nickel (75 g/L). Manganese sulfide (MnS) was used to deeply remove copper from the elect...Copper is difficult to separate from nickel electrolyte due to low concentration of copper (0.53 g/L) with high concentration of nickel (75 g/L). Manganese sulfide (MnS) was used to deeply remove copper from the electrolyte. Experimental results show that the concentration of copper (ρ(Cu)) decreases from 530 to 3 mg/L and the mass ratio of copper to nickel (RCu/Ni) in the residue reaches above 15 when the MnS dosage is 1.4 times the theoretical valueDt,MnS (Dt,MnS=0.74 g) and the pH value of electrolyte is 4?5 with reaction time more than 60 min at temperatures above 60 °C. The concentration of newly generated Mn2+(ρ(Mn)) in the solution is also reduced to 3 mg/L by the oxidation reaction. The values ofρ(Cu),ρ(Mn)andRCu/Ni meet the requirements of copper removal from the electrolyte. It is shown that MnS can be considered a highly effective decoppering reagent.展开更多
Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte inte...Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.展开更多
Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrit...Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.展开更多
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv...Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.展开更多
In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid...In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid solution atoms in theα-Mg matrix without its second-phase generation,and at the same time facilitates grain refinement,dendritic segregation and Mg17Sr2-phases precipitation.During discharge operation,Sr modifies the film composition via its compounds and promoted the redeposition of In at the substrate/film interface;their co-deposition behavior on the anodic reaction surface enhances anode reaction kinetics,suppresses the negative difference effect(NDE)and mitigates the“chunk effect”(CE),which is contributed to uniform dissolution and low self-corrosion hydrogen evolution rate(HER).Therefore,Mg-Sr-xIn alloy anodes show excellent discharge performance,e.g.,0.5Sr-1.0In shows an average discharge voltage of 1.4234 V and a specific energy density of 1990.71 Wh kg^(-1)at 10 mA cm^(-2).Furthermore,the decisive factor(CE and self-discharge HE)for anodic efficiency are quantitively analyzed,the self-discharge is the main factor of cell efficiency loss.Surprisingly,all Mg-Sr-xIn anodes show anodic efficiency greater than 60%at high current density(≥10 mA cm^(-2)),making them excellent candidate anodes for Mg-Air cells at high-power output.展开更多
Tailoring functional interfacial layers through molecular design of electrolyte additives has emerged as a prevalent strategy to modulate interfacial reactions and stabilize aqueous zinc-ion batteries(AZIBs).In this w...Tailoring functional interfacial layers through molecular design of electrolyte additives has emerged as a prevalent strategy to modulate interfacial reactions and stabilize aqueous zinc-ion batteries(AZIBs).In this work,the effect of alkyl chain-induced conformation evolution in interfacial layers on stabilizing the zinc anode was systematically studied using linear cationic surfactant additives.Based on the electrochemical tests and COMSOL simulations,these additives expanded the electrochemical stability window of electrolytes and formed zincophilic-hydrophobic interfacial layers on the anode surface,thus suppressing side reactions and blocking water erosion.Moreover,the interfacial layers not only increased the nucleation overpotential of zinc ions,thus alleviating the electrolyte concentration polarization,but also restricted the 2D diffusion of zinc ions on the anode surface,thereby inducing uniform deposition of finer zinc particles and inhibiting dendrite growth.Furthermore,theoretical calculations revealed that va rying alkyl chain lengths in cationic surfactants and their adsorption configurations resulted in different interfacial layer thicknesses.Especially the dodecyltrimethylammonium chloride(DTAC),the dodecyl group provided a robust hydrophobic layer,effectively stabilizing the zinc anode.And the Zn‖Zn cell with ZSO-DTAC electrolyte achieved a long lifespan of 2000 h at 1 mA cm^(-2),the Zn‖Cu cell exhibited an excellent Coulombic efficiency of 99.69%at 2 mA cm^(-2).In addition,the Zn‖MnO_(2) full cell delivered an initial capacity of 149.44 mA h g^(-1)at 5 A g^(-1),with 83.02%capacity retention after 2000cycles.This work provided fundamental insights into modulating interfacial conformations and reactions to stabilize zinc anodes by surfactant-type additives,offering practical guidance for electrolyte optimization in high-performance AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
In order to establish a simple,sensitive,and fast reliable detection method to determine the magnolol,FeWO4 nanoflower was synthesised through a solvothermal technique and FeWO4 nanoflower modified carbon paste electr...In order to establish a simple,sensitive,and fast reliable detection method to determine the magnolol,FeWO4 nanoflower was synthesised through a solvothermal technique and FeWO4 nanoflower modified carbon paste electrode（CPE） was developed.The voltammetric behavior of magnolol on the modified electrodes was studied using cyclic voltammetry（CV）,linear sweep voltammetry（LSV）,and differential pulse voltammetry（DPV）.The experimental results showed that the modified electrode remarkably enhanced the electrochemical response of the magnolol and exhibited a wide linear range for determination of the magnolol from 1.0×10-7 to 1.0×10-4 mol/L with a low detection limit of 5.0×10-8 mol/L.展开更多
While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further devel...While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further development dramatically.Herein,we utilize the amino acid glycine(Gly)as an electrolyte additive to stabilize the Zn anode–electrolyte interface.The unique interfacial chemistry is facilitated by the synergistic“anchor-capture”effect of polar groups in Gly molecule,manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn^(2+)in the local region.As such,this robust anode–electrolyte interface inhibits the disordered migration of Zn^(2+),and effectively suppresses both side reactions and dendrite growth.The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22%at 1 mA cm^(−2)and 0.5 mAh cm^(−2)over 500 cycles.Even at a high Zn utilization rate(depth of discharge,DODZn)of 68%,a steady cycle life up to 200 h is obtained for ultrathin Zn foils(20μm).The superior rate capability and long-term cycle stability of Zn–MnO_(2)full cells further prove the effectiveness of Gly in stabilizing Zn anode.This work sheds light on additive designing from the specific roles of polar groups for AZIBs.展开更多
We prepared Pb-0.3wt%Ag/Pb-WC（WC stands for tungsten carbide,the same below） composite inert anodes by double-pulse electrodeposition on the surface of Pb-0.3wt%Ag substrates,and investigated the electrochemical pro...We prepared Pb-0.3wt%Ag/Pb-WC（WC stands for tungsten carbide,the same below） composite inert anodes by double-pulse electrodeposition on the surface of Pb-0.3wt%Ag substrates,and investigated the electrochemical properties of the composite inert anodes,which were obtained under different forward pulse average current densities from 2 A/dm2 to 5 A/dm2 and WC concentrations from 0 g/L to 40 g/L in bath.The kinetic parameters of oxygen evolution,corrosion potential and corrosion current of the composite inert anodes were obtained in a synthetic zinc electrowinning electrolyte of 50 g/L Zn2＋ and 150 g/L H2SO4 at 35 ℃,by measuring the anodic polarization curves,Tafel polarization curves and cyclic voltammetry curves.The results show that Pb-0.3wt% Ag/Pb-WC composite inert anodes obtained under forward pulse average current density of 3 A/dm2 and WC concentration of 30 g/L in an original acid plating bath,possess higher electrocatalytic activity of oxygen evolution,lower overpotential of oxygen evolution,better reversibility of electrode reaction and corrosion resistance in [ZnSO4＋H2SO4] solution.The overpotential of oxygen evolution of the composite inert anode is 0.926 V under 500 A/m2 in [ZnSO4＋H2SO4] solution,and 245 mV lower than that of Pb-1% Ag alloy;the corrosion current of the composite inert anode is 0.95×10-4A which is distinctly lower than that of Pb-1%Ag alloy,showing the excellent corrosion resistance.展开更多
In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond（BDD） anodes was investigated in different electrolytes. A complete mineraliz...In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond（BDD） anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in Na Cl;however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and Na Cl O4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine（Cl2, HCl O, Cl O-）electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density（≤ 10 m A/cm2） and neutral medium（p H in the range 6–9） should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate.展开更多
An efficient and convenient synthesis of 1,4-dihydropyrano[2,3-c]pyrazole derivatives is described,using the electrogenerated anion of ethanol as the base in the presence of sodium bromide as an supporting electrolyte...An efficient and convenient synthesis of 1,4-dihydropyrano[2,3-c]pyrazole derivatives is described,using the electrogenerated anion of ethanol as the base in the presence of sodium bromide as an supporting electrolyte in a one-pot, three component condensation of malononitrile, aromatic aldehydes and 3-methyl-1-phenyl-1H-pyrazol-5（4H）-one. The reaction is carried out in an undivided cell containing an iron electrode as the cathode and a graphite electrode as the anode, at a constant current at room temperature.展开更多
基金supported by the National Natural Science Foundation of China(52402316)the Natural Science Foundation of Zhejiang Province(LQ23B030002)the Start-up Foundation of Zhejiang University of Science and Technology(ZUST)。
文摘The preferential proton reduction over zinc-ion deposition in aqueous batteries arises from dual yet conflicting roles of water as charge carrier and parasitic reactant,posing persistent interfacial challenges.Although cosolvent engineering has shown promise in mitigating water activity through hydrogenbond network modulation,prevailing strategies remain limited by their narrow focus on electronic and functional group properties,neglecting the stereochemical influence on molecular assembly.In this work,we uncover how molecular chirality dictates the hierarchical organization of hydrogen-bonding networks between cosolvents and water,which is a critical but previously unrecognized determinant of interfacial stability.By interrogating enantiomeric pairs(L-/D-carnitine),we demonstrate that chiral constraints steer the spatial arrangement of hydration structures through stereoselective hydrogenbonding geometries.Combined spectroscopic and molecular dynamics analyses reveal that L-carnitine(L-CN)forms a three-dimensional hydrogen-bonded matrix with water,exhibiting superior directional connectivity relative to its D-isomer.This stereo-dependent architecture simultaneously reinforces Zn2+solvation shells via bridging H-bond interactions and generates a self-adaptive interfacial structure that kinetically isolates water from the zinc anode surface.This stereochemical optimization enables Zn||Zn symmetric cells with unprecedented cycling stability exceeding 2000 h at 0.5 mA cm^(-2)/0.5 mAh cm^(-2).Corresponding Zn||Cu asymmetric cells maintain a high average Coulombic efficiency of 99.7%over 500 cycles at 3.0 mA cm^(-2)/3.0 mAh cm^(-2).This study pioneers a stereochemical design framework for aqueous electrolytes,elucidating chiral recognition mechanisms in solvation structures and establishing molecular topology engineering as a transformative strategy for high-efficiency energy storage systems.
基金Project(51104183)supported by the National Natural Science Foundation of ChinaProject supported by the China Scholarship Council
文摘Copper is difficult to separate from nickel electrolyte due to low concentration of copper (0.53 g/L) with high concentration of nickel (75 g/L). Manganese sulfide (MnS) was used to deeply remove copper from the electrolyte. Experimental results show that the concentration of copper (ρ(Cu)) decreases from 530 to 3 mg/L and the mass ratio of copper to nickel (RCu/Ni) in the residue reaches above 15 when the MnS dosage is 1.4 times the theoretical valueDt,MnS (Dt,MnS=0.74 g) and the pH value of electrolyte is 4?5 with reaction time more than 60 min at temperatures above 60 °C. The concentration of newly generated Mn2+(ρ(Mn)) in the solution is also reduced to 3 mg/L by the oxidation reaction. The values ofρ(Cu),ρ(Mn)andRCu/Ni meet the requirements of copper removal from the electrolyte. It is shown that MnS can be considered a highly effective decoppering reagent.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the National Natural Science Foundation of China(No.U23A20555,52202211)+3 种基金the Ninth Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Chongqing Technology Innovation and Application Development Project(No.CSTB2022TIAD-KPX0028)the Fundamental Research Funds for the Central Universities(2023CDJXY-018)the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2022119,cx2023087).
文摘Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.
基金financially supported by the National Natural Science Foundation of China (No. 52377222)the Natural Science Foundation of Hunan Province, China (Nos. 2023JJ20064, 2023JJ40759)。
文摘Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.
基金supported by the National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22379013 and 22209010)the Beijing Institute of Technology“Xiaomi Young Scholars”program。
文摘Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.
文摘In this work,the combined addition of strontium/indium(Sr/In)to the magnesium anode for Mg-Air Cells is investigated to improve discharge performance by modifying the anode/electrolyte interface.Indium exists as solid solution atoms in theα-Mg matrix without its second-phase generation,and at the same time facilitates grain refinement,dendritic segregation and Mg17Sr2-phases precipitation.During discharge operation,Sr modifies the film composition via its compounds and promoted the redeposition of In at the substrate/film interface;their co-deposition behavior on the anodic reaction surface enhances anode reaction kinetics,suppresses the negative difference effect(NDE)and mitigates the“chunk effect”(CE),which is contributed to uniform dissolution and low self-corrosion hydrogen evolution rate(HER).Therefore,Mg-Sr-xIn alloy anodes show excellent discharge performance,e.g.,0.5Sr-1.0In shows an average discharge voltage of 1.4234 V and a specific energy density of 1990.71 Wh kg^(-1)at 10 mA cm^(-2).Furthermore,the decisive factor(CE and self-discharge HE)for anodic efficiency are quantitively analyzed,the self-discharge is the main factor of cell efficiency loss.Surprisingly,all Mg-Sr-xIn anodes show anodic efficiency greater than 60%at high current density(≥10 mA cm^(-2)),making them excellent candidate anodes for Mg-Air cells at high-power output.
基金funding provided by Cangzhou Institute of Tiangong University(Grant No.TGCYY-F-0301)Hebei Natural Science Foundation,China(Grant No.E2025110039)。
文摘Tailoring functional interfacial layers through molecular design of electrolyte additives has emerged as a prevalent strategy to modulate interfacial reactions and stabilize aqueous zinc-ion batteries(AZIBs).In this work,the effect of alkyl chain-induced conformation evolution in interfacial layers on stabilizing the zinc anode was systematically studied using linear cationic surfactant additives.Based on the electrochemical tests and COMSOL simulations,these additives expanded the electrochemical stability window of electrolytes and formed zincophilic-hydrophobic interfacial layers on the anode surface,thus suppressing side reactions and blocking water erosion.Moreover,the interfacial layers not only increased the nucleation overpotential of zinc ions,thus alleviating the electrolyte concentration polarization,but also restricted the 2D diffusion of zinc ions on the anode surface,thereby inducing uniform deposition of finer zinc particles and inhibiting dendrite growth.Furthermore,theoretical calculations revealed that va rying alkyl chain lengths in cationic surfactants and their adsorption configurations resulted in different interfacial layer thicknesses.Especially the dodecyltrimethylammonium chloride(DTAC),the dodecyl group provided a robust hydrophobic layer,effectively stabilizing the zinc anode.And the Zn‖Zn cell with ZSO-DTAC electrolyte achieved a long lifespan of 2000 h at 1 mA cm^(-2),the Zn‖Cu cell exhibited an excellent Coulombic efficiency of 99.69%at 2 mA cm^(-2).In addition,the Zn‖MnO_(2) full cell delivered an initial capacity of 149.44 mA h g^(-1)at 5 A g^(-1),with 83.02%capacity retention after 2000cycles.This work provided fundamental insights into modulating interfacial conformations and reactions to stabilize zinc anodes by surfactant-type additives,offering practical guidance for electrolyte optimization in high-performance AZIBs.
基金supported by the Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金Funded by the National Natural Science Foundation of China(Nos.21461008 and 21465009)the Open Foundation of Key Laboratory of Biologic Resources Protection and Utilization of Hubei Province,Forestry Key Discipline(No.PKLHB1303)the Hubei University for Nationalities(No.MY2009B007)
文摘In order to establish a simple,sensitive,and fast reliable detection method to determine the magnolol,FeWO4 nanoflower was synthesised through a solvothermal technique and FeWO4 nanoflower modified carbon paste electrode（CPE） was developed.The voltammetric behavior of magnolol on the modified electrodes was studied using cyclic voltammetry（CV）,linear sweep voltammetry（LSV）,and differential pulse voltammetry（DPV）.The experimental results showed that the modified electrode remarkably enhanced the electrochemical response of the magnolol and exhibited a wide linear range for determination of the magnolol from 1.0×10-7 to 1.0×10-4 mol/L with a low detection limit of 5.0×10-8 mol/L.
基金supported by National Key R&D Program(2022YFB2502000)Zhejiang Provincial Natural Science Foundation of China(LZ23B030003)+1 种基金the Fundamental Research Funds for the Central Universities(2021FZZX001-09)the National Natural Science Foundation of China(52175551).
文摘While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further development dramatically.Herein,we utilize the amino acid glycine(Gly)as an electrolyte additive to stabilize the Zn anode–electrolyte interface.The unique interfacial chemistry is facilitated by the synergistic“anchor-capture”effect of polar groups in Gly molecule,manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn^(2+)in the local region.As such,this robust anode–electrolyte interface inhibits the disordered migration of Zn^(2+),and effectively suppresses both side reactions and dendrite growth.The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22%at 1 mA cm^(−2)and 0.5 mAh cm^(−2)over 500 cycles.Even at a high Zn utilization rate(depth of discharge,DODZn)of 68%,a steady cycle life up to 200 h is obtained for ultrathin Zn foils(20μm).The superior rate capability and long-term cycle stability of Zn–MnO_(2)full cells further prove the effectiveness of Gly in stabilizing Zn anode.This work sheds light on additive designing from the specific roles of polar groups for AZIBs.
基金Funded by the Specialized Research Fund for the Doctoral Program of the Ministry of Education of China(No.20125314110011)the Key Project of Yunnan Province Applied Basic Research Plan of China(No.2014FA024)the National Natural Science Foundation of China(No.51564029)
文摘We prepared Pb-0.3wt%Ag/Pb-WC（WC stands for tungsten carbide,the same below） composite inert anodes by double-pulse electrodeposition on the surface of Pb-0.3wt%Ag substrates,and investigated the electrochemical properties of the composite inert anodes,which were obtained under different forward pulse average current densities from 2 A/dm2 to 5 A/dm2 and WC concentrations from 0 g/L to 40 g/L in bath.The kinetic parameters of oxygen evolution,corrosion potential and corrosion current of the composite inert anodes were obtained in a synthetic zinc electrowinning electrolyte of 50 g/L Zn2＋ and 150 g/L H2SO4 at 35 ℃,by measuring the anodic polarization curves,Tafel polarization curves and cyclic voltammetry curves.The results show that Pb-0.3wt% Ag/Pb-WC composite inert anodes obtained under forward pulse average current density of 3 A/dm2 and WC concentration of 30 g/L in an original acid plating bath,possess higher electrocatalytic activity of oxygen evolution,lower overpotential of oxygen evolution,better reversibility of electrode reaction and corrosion resistance in [ZnSO4＋H2SO4] solution.The overpotential of oxygen evolution of the composite inert anode is 0.926 V under 500 A/m2 in [ZnSO4＋H2SO4] solution,and 245 mV lower than that of Pb-1% Ag alloy;the corrosion current of the composite inert anode is 0.95×10-4A which is distinctly lower than that of Pb-1%Ag alloy,showing the excellent corrosion resistance.
文摘In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond（BDD） anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in Na Cl;however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and Na Cl O4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine（Cl2, HCl O, Cl O-）electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density（≤ 10 m A/cm2） and neutral medium（p H in the range 6–9） should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate.
基金University of Sistan and baluchestanPayame Noor University
文摘An efficient and convenient synthesis of 1,4-dihydropyrano[2,3-c]pyrazole derivatives is described,using the electrogenerated anion of ethanol as the base in the presence of sodium bromide as an supporting electrolyte in a one-pot, three component condensation of malononitrile, aromatic aldehydes and 3-methyl-1-phenyl-1H-pyrazol-5（4H）-one. The reaction is carried out in an undivided cell containing an iron electrode as the cathode and a graphite electrode as the anode, at a constant current at room temperature.
