Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the c...Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the challenges inherent in zinc(Zn) anode,namely dendrite formation and interfacial parasitic reactions,have greatly impeded their practical application.Whereas the critical issue of dendrite formation has attracted widespread concern,the parasitic reactions of Zn anodes with mildly acidic electrolytes have received very little attentions.Considering that the low Zn reversibility that stems from interfacial parasitic reactions is the major obstacle to the commercialization of ZIBs,thorough understanding of these side reactions and the development of correlative inhibition strategies are significant.Therefore,in this review,the brief fundamentals of corrosion and hydrogen evolution reactions at Zn surface is presented.In addition,recent advances and research efforts addressing detrimental side reactions are reviewed from the perspective of electrode design,electrode-electrolyte interfacial engineering and electrolyte modification.To facilitate the future researches on this aspect,perspectives and suggestions for relevant investigations are provided lastly.展开更多
The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electro...The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).展开更多
Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions...Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions.Whereas most of protective layers are complex and costly,making commercial applications challenging.Herein,we introduce a facile method involving the addition of CuCl_(2) electrolyte additives to conventional electrolyte systems,which,through rapid displacement reactions and controlled electrochemical cycling,forms a CuZn_(5) alloy layer with 97.2%lattice matching to the(002)plane(CuZn_(5)@Zn),thus regulating the(002)plane epitaxial deposition.As a result,the symmetric cells with CuZn_(5)@Zn demonstrate an ultra-long cycle life of 3600 h at 1 mA cm^(-2).Under extreme conditions of high current density(20 m A cm^(-2))and high zinc utilization(DOD_(Zn)=50%),stable cycling performance is maintained for 220 and 350 h,respectively.Furthermore,the CuZn_(5)@Zn||NH_(4)V_(4)O_(10)full cell maintains a capacity of 120 m A h g^(-1)even after 10,000 cycles at a high current density of 10 A g^(-1).This work presents a facile and efficient strategy for constructing stable metal anode materials,with implications for the development of next-generation rechargeable batteries.展开更多
Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limi...Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limited surface area and severe interfacial issues including metallic dendrites and corrosion side reactions,limiting the depth of discharge(DOD)of the foil electrode materials.Herein,a low-temperature replacement reaction is utilized to in-situ construct a three-dimensional(3D)corrosion-resistant interface for deeply rechargeable Zn foil electrodes.Specifically,the deliberate low-temperature environment controlled the replacement rate between polycrystalline Zn metal and oxalic acid,producing a Zn foil electrode with distinct 3D corrosion-resistant interface(3DCI-Zn),which differed from conventional two-dimensional(2D)protective structure and showed an order of magnitude higher surface area.Consequently,the 3DCI-Zn electrode exhibited dendrite-free and anticorrosion properties,and achieved stable plating/stripping performance for 1000 h at 10 mA cm^(-2)and 10 mAh cm^(-2)with a remarkable DOD of 79%.After pairing with a MnO2cathode with a high areal capacity of 4.2 mAh cm^(-2),the pouch cells delivered 168 Wh L^(-1)and a capacity retention of 89.7%after 100 cycles with a low negative/positive(N/P)ratio of 3:1.展开更多
Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes e...Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes exhibit a limited-service life and inferior reversibility owing to the issues of Zn dendrites and side reactions,which severely hinder the further development of RAZIBs.Researchers have attempted to design high-performance Zn anodes by interfacial engineering,including surface modification and the addition of electrolyte additives,to stabilize Zn anodes.The purpose is to achieve uniform Zn nucleation and flat Zn deposition by regulating the deposition behavior of Zn ions,which effectively improves the cycling stability of the Zn anode.This review comprehensively summarizes the reaction mechanisms of interfacial modification for inhibiting the growth of Zn dendrites and the occurrence of side reactions.In addition,the research progress of interfacial engineering strategies for RAZIBs is summarized and classified.Finally,prospects and suggestions are provided for the design of highly reversible Zn anodes.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
Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the ...Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.展开更多
基金financially supported by the National Key R&D Program of China (grant no. 2018YFB0905400)the National Natural Science Foundation of China (grant nos. 22075331, 51702376, 21905057)+2 种基金the Fundamental Research Funds for the Central Universities (19lgzd02)the Guangdong Pearl River Talents Plan (2019QN01L117)the National Thousand Youth Talents Project of the Chinese Government.
文摘Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the challenges inherent in zinc(Zn) anode,namely dendrite formation and interfacial parasitic reactions,have greatly impeded their practical application.Whereas the critical issue of dendrite formation has attracted widespread concern,the parasitic reactions of Zn anodes with mildly acidic electrolytes have received very little attentions.Considering that the low Zn reversibility that stems from interfacial parasitic reactions is the major obstacle to the commercialization of ZIBs,thorough understanding of these side reactions and the development of correlative inhibition strategies are significant.Therefore,in this review,the brief fundamentals of corrosion and hydrogen evolution reactions at Zn surface is presented.In addition,recent advances and research efforts addressing detrimental side reactions are reviewed from the perspective of electrode design,electrode-electrolyte interfacial engineering and electrolyte modification.To facilitate the future researches on this aspect,perspectives and suggestions for relevant investigations are provided lastly.
基金financially supported by the Natural Sciences and Engineering Research Council of Canada (NSERC),through the Discovery Grant Program (RGPIN-2018-06725)the Discovery Accelerator Supplement Grant program (RGPAS-2018-522651)+2 种基金the New Frontiers in Research Fund-Exploration program (NFRFE-2019-00488)supported by funding from the Canada First Research Excellence Fund as part of the University of Alberta’s Future Energy Systems research initiative (FES-T06-Q03)supported by the Chinese Scholarship Council (CSC)(Grant No. 202006450027).
文摘The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).
基金financially supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(Grant no.52125405 and U22A20108)+4 种基金the support from the Hubei Provincial Natural Science Foundation of China(Grant No.2023AFB155)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(opening project number:202401,202404)the Thailand Science Research and Innovation Fund Chulalongkorn University(INDF67620003)the National Science,Research and Innovation Fund(NSRF)via the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(Grant no.B05F640153)the National Research Council of Thailand(NRCT)and Chulalongkorn University(N42A660383)。
文摘Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions.Whereas most of protective layers are complex and costly,making commercial applications challenging.Herein,we introduce a facile method involving the addition of CuCl_(2) electrolyte additives to conventional electrolyte systems,which,through rapid displacement reactions and controlled electrochemical cycling,forms a CuZn_(5) alloy layer with 97.2%lattice matching to the(002)plane(CuZn_(5)@Zn),thus regulating the(002)plane epitaxial deposition.As a result,the symmetric cells with CuZn_(5)@Zn demonstrate an ultra-long cycle life of 3600 h at 1 mA cm^(-2).Under extreme conditions of high current density(20 m A cm^(-2))and high zinc utilization(DOD_(Zn)=50%),stable cycling performance is maintained for 220 and 350 h,respectively.Furthermore,the CuZn_(5)@Zn||NH_(4)V_(4)O_(10)full cell maintains a capacity of 120 m A h g^(-1)even after 10,000 cycles at a high current density of 10 A g^(-1).This work presents a facile and efficient strategy for constructing stable metal anode materials,with implications for the development of next-generation rechargeable batteries.
基金financially supported by the National Natural Science Foundation of China (No.22205068,22109144)the“CUG Scholar”Scientific Research Funds at China University of Geosciences (Wuhan) (Project No.2022118)the Fundamental Research Funds for the Central Universities,China University of Geosciences (Wuhan) (No.162301202673)。
文摘Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limited surface area and severe interfacial issues including metallic dendrites and corrosion side reactions,limiting the depth of discharge(DOD)of the foil electrode materials.Herein,a low-temperature replacement reaction is utilized to in-situ construct a three-dimensional(3D)corrosion-resistant interface for deeply rechargeable Zn foil electrodes.Specifically,the deliberate low-temperature environment controlled the replacement rate between polycrystalline Zn metal and oxalic acid,producing a Zn foil electrode with distinct 3D corrosion-resistant interface(3DCI-Zn),which differed from conventional two-dimensional(2D)protective structure and showed an order of magnitude higher surface area.Consequently,the 3DCI-Zn electrode exhibited dendrite-free and anticorrosion properties,and achieved stable plating/stripping performance for 1000 h at 10 mA cm^(-2)and 10 mAh cm^(-2)with a remarkable DOD of 79%.After pairing with a MnO2cathode with a high areal capacity of 4.2 mAh cm^(-2),the pouch cells delivered 168 Wh L^(-1)and a capacity retention of 89.7%after 100 cycles with a low negative/positive(N/P)ratio of 3:1.
基金financially supported by the National Natural Science Foundation of China(Nos.51872090,51772097,51972346)the Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433)+3 种基金the Natural Science Foundation of Hebei Province(No.E2020209151)the Hunan Natural Science Fund for Distinguished Young Scholar(2021JJ10064)the Program of Youth Talent Support for Hunan Province(2020RC3011)the Innovation-Driven Project of Central South University(No.2020CX024).
文摘Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes exhibit a limited-service life and inferior reversibility owing to the issues of Zn dendrites and side reactions,which severely hinder the further development of RAZIBs.Researchers have attempted to design high-performance Zn anodes by interfacial engineering,including surface modification and the addition of electrolyte additives,to stabilize Zn anodes.The purpose is to achieve uniform Zn nucleation and flat Zn deposition by regulating the deposition behavior of Zn ions,which effectively improves the cycling stability of the Zn anode.This review comprehensively summarizes the reaction mechanisms of interfacial modification for inhibiting the growth of Zn dendrites and the occurrence of side reactions.In addition,the research progress of interfacial engineering strategies for RAZIBs is summarized and classified.Finally,prospects and suggestions are provided for the design of highly reversible Zn anodes.
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.
文摘Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.
