Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.展开更多
Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabrica...Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.展开更多
Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(...Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.展开更多
采用水热合成法制备核壳结构Zn/HZSM-5_((Si/Al=25))@HZSM-5_((Si/Al=200))催化剂,并考察其甲醇制芳烃(Methanol to Aromatics,MTA)反应性能,重点研究壳层包覆对催化剂积碳行为及催化寿命的影响。结果表明,高Si/Al壳层催化剂其低酸量可...采用水热合成法制备核壳结构Zn/HZSM-5_((Si/Al=25))@HZSM-5_((Si/Al=200))催化剂,并考察其甲醇制芳烃(Methanol to Aromatics,MTA)反应性能,重点研究壳层包覆对催化剂积碳行为及催化寿命的影响。结果表明,高Si/Al壳层催化剂其低酸量可抑制含氧积碳生成;壳层对核层的包覆作用可从根本上阻断核层催化剂上含氧积碳的生成;核壳结构的构筑可调变催化剂积碳行为,催化剂失活速率降低,催化稳定性和芳构化性能明显增强,在反应温度T=400℃,甲醇空速WHSV=1.2 h^(-1)的反应条件下,Zn/HZSM-5@HZSM-5核壳催化剂的催化寿命达210 h,起始轻质芳烃(BTX)选择性达46.2%且反应138 h后仍高达20%以上。展开更多
基金supported by the Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
基金(partially)funded by the BK21 FOUR Program of Graduate School,Kyung Hee University(GS-1-JO-ON-info2120241890)。
文摘Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.
基金supported by the National Natural Science Foundation of China(22269020,42167068,U23A20582)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17,2023CYZC-68)+1 种基金the Key Project of Natural Science Foundation of Gansu Province(25JRRA004)2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10).
文摘Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.
