Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth...Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.展开更多
Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to...Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.展开更多
The practical application of emerging rechargeable aqueous zinc(Zn)batteries is challenged by the poor reversibility and cycling stability of Zn anodes,primarily due to parasitic side reactions.While numerous strategi...The practical application of emerging rechargeable aqueous zinc(Zn)batteries is challenged by the poor reversibility and cycling stability of Zn anodes,primarily due to parasitic side reactions.While numerous strategies have been proposed,balancing the suppression of side reactions with the maintenance of fast Zn plating/stripping kinetics remains a significant challenge.In this study,sucrose,a sterically-hindered organic molecule with abundant hydroxyl groups,is employed to suppress the side reactions and maintain the moderate kinetics of Zn plating/stripping by modulating the hydrogen bond network without altering the Zn^(2+)solvation structure.Its steric hindrance effect further impedes the lateral diffusion of Zn atoms on the electrode surface within the electric double layer,effectively mitigating dendrite growth and stabilizing the electrodeposition process.Consequently,the formulated Suc/ZnSO_(4)electrolyte achieves a remarkably Coulombic efficiency of 99.90% over 2600 cycles at 3 mA cm^(-2)for 1 mAh cm^(-2)in Zn‖Cu cells.The enhanced Zn anode reversibility leads to excellent cycling stability in Zn‖LiFePO_(4)cells and Zn‖β-MnO_(2)cells.This study underscores the potential of sterically-hindered organic molecule strategies to enhance Zn anode stability while maintaining favorable Zn deposition/stripping dynamics in aqueous Zn batteries.展开更多
Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of ...Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of zinc anodes.Herein,we report an electrolyte additive-assembled interconnecting molecules-zinc anode interface,realizing highly stable and fast-kinetics zinc anodes for ZHSs.The sulfobutyl groups-graftedβ-cyclodextrin(SC)supramolecules as a trace additive in ZnSO_(4)electrolytes not only adsorb on zinc anodes but also self-assemble into an interconnecting molecule interface benefiting from the mutual attraction between the electron-rich sulfobutyl group and the electron-poor cavity of the adjacent SC supramolecule.The interconnecting molecules-zinc anode interface provides abundant anion-trapping cavities and zincophilic groups to enhance Zn^(2+)transference number and homogenize Zn^(2+)deposition sites,and meanwhile,it accelerates the desolvation of hydrated Zn^(2+)to improve zinc deposition kinetics and inhibit active water molecules from inducing parasitic reactions at the zinc deposition interface,making zinc anodes present superior reversibility with 99.7%Coulombic efficiency,~30 times increase in operation lifetime and an outstanding cumulative capacity at large current densities.ZHSs with 20,000-cycle life and optimized rate capability are thereby achieved.This work provides an inspiring strategy for designing zinc anode interfaces to promote the development of ZHSs.展开更多
Aqueous zinc-ion batteries are highly favored for their enhanced safety and reduced cost.However,there exist challenges including zinc dendrite,hydrogen evolution,and surface corrosion to be solved.Using electrolyte a...Aqueous zinc-ion batteries are highly favored for their enhanced safety and reduced cost.However,there exist challenges including zinc dendrite,hydrogen evolution,and surface corrosion to be solved.Using electrolyte additives is a highly convenient approach to solving zinc anode-related issues.Inspired by industrial corrosion protection,a trace amount of the corrosion inhibitor urotropine(URT)is used as an electrolyte additive to protect the zinc anode.Theoretical calculation and experimental analysis confirm the adsorption of URT molecules onto the surface of Zn,which inhibits hydrogen evolution.This adsorption further leads to the formation of an inorganic-organic bilayer solid electrolyte interface(SEI)on the surface of the zinc anode,effectively protecting the Zn anode from corrosion,hydrogen evolution and zinc dendrites.The presence of SEI enables symmetrical Zn//Zn cells to exhibit a long cycling performance of 1750 h at 1mA/cm^(2)and an average coulombic efficiency of 99.0%at 1mA/cm^(2)in Zn//Cu cells.After being coupled with polyaniline(PANI),the Zn//PANI full battery displays excellent cycle stability and specific capacity.展开更多
Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growt...Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growth.To address this issue,an effective strategy is to construct a functional solid electrolyte interface(SEI)in situ.However,this is substantially challenging owing to the severe hydrogen evolution reaction(HER)and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes.Herein,we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reductionchemical precipitation approach.By chemically capturing the hydroxide ions(OH-)from HER,fatty acid methyl ester ethoxylate(FMEE),as an aqueous electrolyte additive,undergoes ester group hydrolysis following by a combination with Zn^(2+)to form insoluble fatty acid-zinc,enabling intelligent growth of a SEI on the Zn anode surface.As a result,the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 m A/cm^(2)and 1 m Ah/cm^(2).The Zn-V_(2)O_(5)full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability.This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes,advancing the development of high-performance aqueous batteries.展开更多
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
Biocompatible devices are widely employed in modernized lives and medical fields in the forms of wearable and implantable devices,raising higher requirements on the battery biocompatibility,high safety,low cost,and ex...Biocompatible devices are widely employed in modernized lives and medical fields in the forms of wearable and implantable devices,raising higher requirements on the battery biocompatibility,high safety,low cost,and excellent electrochemical performance,which become the evaluation criteria toward developing feasible biocompatible batteries.Herein,through conducting the battery implantation tests and leakage scene simulations on New Zealand rabbits,zinc sulfate electrolyte is proved to exhibit higher biosecurity and turns out to be one of the ideal zinc salts for biocompatible zinc-ion batteries(ZIBs).Furthermore,in order to mitigate the notorious dendrite growth and hydrogen evolution in mildly acidic electrolyte as well as improve their operating stability,Sn hetero nucleus is introduced to stabilize the zinc anode,which not only facilitates the planar zinc deposition,but also contributes to higher hydrogen evolution overpotential.Finally,a long lifetime of 1500 h for the symmetrical cell,the specific capacity of 150 mAh g^(-1)under 0.5 A g^(-1)for the Zn-MnO_(2)battery and 212 mAh g^(-1)under 5 A g^(-1)for the Zn—NH4V4O10 battery are obtained.This work may provide unique perspectives on biocompatible ZIBs toward the biosecurity of their cell components.展开更多
To tackle energy crisis and achieve sustainable development, aqueous rechargeable zinc ion batteries have gained widespread attention in large-scale energy storage for their low cost, high safety, high theoretical cap...To tackle energy crisis and achieve sustainable development, aqueous rechargeable zinc ion batteries have gained widespread attention in large-scale energy storage for their low cost, high safety, high theoretical capacity, and environmental compatibility in recent years. However, zinc anode in aqueous zinc ion batteries is still facing several challenges such as dendrite growth and side reactions(e.g., hydrogen evolution), which cause poor reversibility and the failure of batteries. To address these issues, interfacial modification of Zn anodes has received great attention by tuning the interaction between the anode and the electrolyte. Herein, we present recent advances in the interfacial modification of zinc anode in this review. Besides, the challenges of reported approaches of interfacial modification are also discussed.Finally, we provide an outlook for the exploration of novel zinc anode for aqueous zinc ion batteries.We hope that this review will be helpful in designing and fabricating dendrite-free and hydrogenevolution-free Zn anodes and promoting the practical application of aqueous rechargeable zinc ion batteries.展开更多
The last several years have witnessed the prosperous development of zinc-ion batteries(ZIBs),which are considered as a promising competitor of energy storage systems thanks to their low cost and high safety.However,th...The last several years have witnessed the prosperous development of zinc-ion batteries(ZIBs),which are considered as a promising competitor of energy storage systems thanks to their low cost and high safety.However,the reversibility and availability of this system are blighted by problems such as uncontrollable dendritic growth,hydrogen evolution,and corrosion passivation on anode side.A functionally and structurally well-designed anode current collectors(CCs)is believed as a viable solution for those problems,with a lack of summarization according to its working mechanisms.Herein,this review focuses on the challenges of zinc anode and the mechanisms of modified anode CCs,which can be divided into zincophilic modification,structural design,and steering the preferred crystal facet orientation.The possible prospects and directions on zinc anode research and design are proposed at the end to hopefully promote the practical application of ZIBs.展开更多
Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given...Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given the limited operability of coating from polymer dispersions,it is imperative to develop simple aqueous-based strategies from monomers for versatile polymer coating.Herein,a Ti_(3)C_(2)Tx MXene-assisted approach is proposed to construct polymer coating on zinc metal surfaces directly from the aqueous solution of monomers in an ice bath.By combining a doctor-blading method with spontaneous polymerization of monomers on the substrates at room temperature,a uniform,adhesive,and versatile coating layer assisted by a small amount of MXene is produced in one step.Additionally,MXene nanosheets serve as nanofillers to further enhance the mechanical strength and ionic conductivity of the polymer coating.Benefiting from good film formation and improved interfacial contact,the coated zinc anode exhibits a long cycling lifespan of over 1900 h.The assembled full cells show excellent cycling stability with a high capacity retention of 85.0%at 16 A g^(-1)over 2600 cycles.This work provides a simple and efficient way to produce polymer coatings directly from monomers,which may give new insights into design multifunctional polymer coatings for various applications.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
Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and h...Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.展开更多
Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.I...Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.In our investigation,we sought to mitigate these issues through the utilization of in situ zinc complex formation reactions to engineer hydrophobic protective layers on the zinc anode surface.These robust interfacial layers serve as effective barriers,isolating the zinc anode from the electrolyte and active water molecules and thereby preventing hydrogen evolution and the generation of undesirable byproducts.Additionally,the presence of numerous zincophilic sites within these protective layers facilitates uniform zinc deposition while concurrently inhibiting dendrite growth.Through comprehensive evaluation of functional anodes featuring diverse functional groups and alkyl chain lengths,we meticulously scrutinized the underlying mechanisms influencing performance variations.This analysis involved precise modulation of interfacial hydrophobicity,rapid Zn^(2+)ion transport,and ordered deposition of Zn^(2+)ions.Notably,the optimized anode,fabricated with octadecylphosphate(OPA),demonstrated exceptional performance characteristics.The Zn//Zn symmetric cell exhibited remarkable longevity,exceeding 4000 h under a current density of 2 mA cm^(-2)and a capacity density of 2 mA h cm^(-2),Furthermore,when integrated with a VOH cathode,the complete cell exhibited superior capacity retention compared to anodes modified with alternative organic molecules.展开更多
Aqueous zinc ion batteries have been considered as the prominent candidate in the next-generation batteries for its low cost,safety and high theoretical capacity.Nonetheless,formation of zinc dendrites and side reacti...Aqueous zinc ion batteries have been considered as the prominent candidate in the next-generation batteries for its low cost,safety and high theoretical capacity.Nonetheless,formation of zinc dendrites and side reactions at the electrode/electrolyte interface during the zinc plating/stripping process affect the cycling reversibility of the zinc anode.Regulation of the zinc plating/stripping process and realizing a highly reversible zinc anode is a great challenge.Herein,we applied a simple and effective approach of controlled-current zinc pre-deposition at copper mesh.At the current density of 40 mA cm^(-2),where the electron/ion transfers are both continuous and balanced,the Zn@CM-40 electrode with the(002)crystal plane orientation and the compactly aligned platelet morphology was successfully obtained.Compared with the zinc foil,the Zn@CM-40 exhibits greatly enhanced reversibility in the repeated plating/stripping(850 h at 1 mA cm^(-2))for the symmetric battery test.A series of characterization techniques including electrochemical analyses,XRD,SEM and optical microscopy observation,were used to demonstrate the correlation between the structure of pre-deposited zinc layer and the cycling stability.The COSMOL Multiphysics modeling demonstrates a more uniform electric field distribution in the Zn@CM than the zinc foil due to the aligned platelet morphology.Furthermore,the significant improvement is also achieved in a Zn||MnO_(2)full battery with a high capacity-retention(87%vs 47.8%).This study demonstrates that controlled-current electrodeposition represents an important strategy to regulate the crystal plane orientation and the morphology of the pre-deposited zinc layer,hence leading to the highly reversible and dendrite-free zinc anode for high-performance zinc ion batteries.展开更多
The uncontrollable dendrites growth and intricately water-induced side reactions occurred on zinc anode leads to safety issues and poor electrochemical kinetics,which largely limit the widespread application of zinc-i...The uncontrollable dendrites growth and intricately water-induced side reactions occurred on zinc anode leads to safety issues and poor electrochemical kinetics,which largely limit the widespread application of zinc-ion batteries(ZIBs).Herein,ethylenediaminetetraacetic acid disodium salt(EDTA-2Na)is utilized as an electrolyte additive to strengthen the reversibility and cycling stability of zinc anode.Experimental results and theoretical calculation demonstrate that the EDTA-2Na presents a much stronger coordination with Zn^(2+)when comparing with H_(2)O molecular,implying the EDTA-2Na is capable to enter the solvation shell of[Zn(OH_(2))_(6)]^(2+)and coordinate with Zn^(2+)ions,thus achieving a flat and smooth zinc deposition with less by-products(Zn_(4)SO_(4)(OH)6·xH_(2)O and H_(2)).Consequently,the zinc symmetric battery with EDTA-2Na additive delivers an excellent cycling stability up to 1800 h under current density of 1 mA cm^(-2),and the hydrogen evolution reaction(HER),corrosion,by-product issues are significantly inhibited.Moreover,the rate performance and stability of coin-type and pouch-type Zn||MnO2/graphite batteries are significantly boosted via EDTA-2Na additive(248 mAh g^(-1)at 0.1 A g^(-1),81.3%after 1000 cycles at a A g^(-1)).This kind of electrolyte additive with chelation and desolvation functions shed lights on strategies of improving zinc anode stability for further application of ZIBs.展开更多
Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion...Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution reaction.Herein,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full batteries.The as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 cycles.Moreover,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 cycles.The high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.展开更多
Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active mate...Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.展开更多
Zinc metal anodes are gaining popularity in aqueous electrochemical energy storage systems for their high safety,cost-effectiveness,and high capacity.However,the service life of zinc metal anodes is severely constrain...Zinc metal anodes are gaining popularity in aqueous electrochemical energy storage systems for their high safety,cost-effectiveness,and high capacity.However,the service life of zinc metal anodes is severely constrained by critical challenges,including dendrites,water-induced hydrogen evolution,and passivation.In this study,a protective two-dimensional metal–organic framework interphase is in situ constructed on the zinc anode surface with a novel gel vapor deposition method.The ultrathin interphase layer(~1μm)is made of layer-stacking 2D nanosheets with angstrom-level pores of around 2.1Å,which serves as an ion sieve to reject large solvent–ion pairs while homogenizes the transport of partially desolvated zinc ions,contributing to a uniform and highly reversible zinc deposition.With the shielding of the interphase layer,an ultra-stable zinc plating/stripping is achieved in symmetric cells with cycling over 1000 h at 0.5 mA cm−2 and~700 h at 1 mA cm^(−2),far exceeding that of the bare zinc anodes(250 and 70 h).Furthermore,as a proof-of-concept demonstration,the full cell paired with MnO_(2) cathode demonstrates improved rate performances and stable cycling(1200 cycles at 1 A g−1).This work provides fresh insights into interphase design to promote the performance of zinc metal anodes.展开更多
Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,hi...Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.展开更多
基金support from the Australian Research Council Discovery Program(DP220103416,DP240102177)Australian Research Council Future Fellowships(FT200100730,FT210100804).
文摘Aqueous zinc(Zn)-ion batteries hold great promise as renewable energy storage system for carbon-neutral energy transition.However,Zn anodes suffer from poor Zn plating/stripping reversibility due to Zn dendrite growth and side reactions.Existing Zn interfacial modification strategies based on single-component or homogeneous structure are insufficient to address these issues comprehensively.Herein,we rationally designed an organic-inorganic hybrid interfacial layer with rigid-to-soft graded structure for dendrite-free and stable Zn anodes.A liquid plasma-assisted oxidation technology is developed to rapidly construct a porous ZnO inner framework in situ.This ZnO layer offers high interfacial energy,mechanical robustness,and an open structure that facilitates ion transport while firmly anchoring a subsequently coated soft polymer layer.The resulting architecture presents a structurally graded and functionally complementary interface,enabling effective dendrite suppression,continuous Zn ion transport,and enhanced corrosion resistance.As a result,a long cycling stability of more than 6000 h can be achieved at 1 mA cm^(-2)for 1 mAh cm^(-2)in symmetric cells.When used as anodes for zinc-iodine full battery,the hybrid interlayer can effectively prevent the Zn anodes from the corrosion by polyiodine,enabling stable cycling and negligible capacity decay(~0.02‰per cycle)for over 10,000 cycles at 2.0 A g^(-1).This work demonstrates a promising interfacial design strategy and introduces a novel liquid plasma-assisted oxidation route for fabricating high-performance Zn anodes towards next-generation aqueous batteries.
基金supported by the Scientific Research and Technology Development Project of China National Petroleum Corporation(Grant Nos.2024ZG50,2022DQ03-03)the National Natural Science Foundation of China(Grant Nos.52372252)the Science and Technology Innovation Program of Hunan Province(Grant Nos.2024RC1022).
文摘Dendrite growth represents one of the most significant challenges that impede the development of aqueous zinc-ion batteries.Herein,Gd^(3+)ions are introduced into conventional electrolytes as a microlevelling agent to achieve dendrite-free zinc electrodeposition.Simulation and experimental results demonstrate that these Gd^(3+)ions are preferentially adsorbed onto the zinc surface,which enables dendritefree zinc anodes by activating the microlevelling effect during electrodeposition.In addition,the Gd^(3+)additives effectively inhibit side reactions and facilitate the desolvation of[Zn(H_(2)O)_(6)]^(2+),leading to highly reversible zinc plating/stripping.Due to these improvements,the zinc anode demonstrates a significantly prolonged cycle life of 2100 h and achieves an exceptional average Coulombic efficiency of 99.72%over 1400 cycles.More importantly,the Zn//NH_(4)V_(4)O_(10)full cell shows a high capacity retention rate of 85.6%after 1000 cycles.This work not only broadens the application of metallic cations in battery electrolytes but also provides fundamental insights into their working mechanisms.
基金funded by the National Key Research and Development Program of China(2022YFB2404500)the Shenzhen Outstanding Talents Training Fund(01090100002)the National Natural Science Foundation of China(52201280)。
文摘The practical application of emerging rechargeable aqueous zinc(Zn)batteries is challenged by the poor reversibility and cycling stability of Zn anodes,primarily due to parasitic side reactions.While numerous strategies have been proposed,balancing the suppression of side reactions with the maintenance of fast Zn plating/stripping kinetics remains a significant challenge.In this study,sucrose,a sterically-hindered organic molecule with abundant hydroxyl groups,is employed to suppress the side reactions and maintain the moderate kinetics of Zn plating/stripping by modulating the hydrogen bond network without altering the Zn^(2+)solvation structure.Its steric hindrance effect further impedes the lateral diffusion of Zn atoms on the electrode surface within the electric double layer,effectively mitigating dendrite growth and stabilizing the electrodeposition process.Consequently,the formulated Suc/ZnSO_(4)electrolyte achieves a remarkably Coulombic efficiency of 99.90% over 2600 cycles at 3 mA cm^(-2)for 1 mAh cm^(-2)in Zn‖Cu cells.The enhanced Zn anode reversibility leads to excellent cycling stability in Zn‖LiFePO_(4)cells and Zn‖β-MnO_(2)cells.This study underscores the potential of sterically-hindered organic molecule strategies to enhance Zn anode stability while maintaining favorable Zn deposition/stripping dynamics in aqueous Zn batteries.
基金the National Key R&D Program of China(2022YFB2404500)Guangdong Basic and Applied Basic Research Foundation(2023A1515110347+2 种基金2023A1515012087)Funding by Science and Technology Projects in Guangzhou(2024A04J3267)the Fundamental Research Funds for the Central Universities(21624411).
文摘Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of zinc anodes.Herein,we report an electrolyte additive-assembled interconnecting molecules-zinc anode interface,realizing highly stable and fast-kinetics zinc anodes for ZHSs.The sulfobutyl groups-graftedβ-cyclodextrin(SC)supramolecules as a trace additive in ZnSO_(4)electrolytes not only adsorb on zinc anodes but also self-assemble into an interconnecting molecule interface benefiting from the mutual attraction between the electron-rich sulfobutyl group and the electron-poor cavity of the adjacent SC supramolecule.The interconnecting molecules-zinc anode interface provides abundant anion-trapping cavities and zincophilic groups to enhance Zn^(2+)transference number and homogenize Zn^(2+)deposition sites,and meanwhile,it accelerates the desolvation of hydrated Zn^(2+)to improve zinc deposition kinetics and inhibit active water molecules from inducing parasitic reactions at the zinc deposition interface,making zinc anodes present superior reversibility with 99.7%Coulombic efficiency,~30 times increase in operation lifetime and an outstanding cumulative capacity at large current densities.ZHSs with 20,000-cycle life and optimized rate capability are thereby achieved.This work provides an inspiring strategy for designing zinc anode interfaces to promote the development of ZHSs.
基金financially supported by Joint Funds of the National Natural Science Foundation of China(No.U22A20140)the National Natural Science Foundation of China(No.22379062)+1 种基金supported by Shenzhen Stable Support Plan Program for Higher Education Institutions Research Program(No.20220816131408001)Shenzhen Science and Technology Program(No.JCYJ20230807091802006)。
文摘Aqueous zinc-ion batteries are highly favored for their enhanced safety and reduced cost.However,there exist challenges including zinc dendrite,hydrogen evolution,and surface corrosion to be solved.Using electrolyte additives is a highly convenient approach to solving zinc anode-related issues.Inspired by industrial corrosion protection,a trace amount of the corrosion inhibitor urotropine(URT)is used as an electrolyte additive to protect the zinc anode.Theoretical calculation and experimental analysis confirm the adsorption of URT molecules onto the surface of Zn,which inhibits hydrogen evolution.This adsorption further leads to the formation of an inorganic-organic bilayer solid electrolyte interface(SEI)on the surface of the zinc anode,effectively protecting the Zn anode from corrosion,hydrogen evolution and zinc dendrites.The presence of SEI enables symmetrical Zn//Zn cells to exhibit a long cycling performance of 1750 h at 1mA/cm^(2)and an average coulombic efficiency of 99.0%at 1mA/cm^(2)in Zn//Cu cells.After being coupled with polyaniline(PANI),the Zn//PANI full battery displays excellent cycle stability and specific capacity.
基金supported by the National Natural Science Foundation of China(No.22309211)the Guangdong Basic and Applied Basic Research Foundation(No.2024A1515010158)+1 种基金the Guangzhou Science and Technology Programme(No.SL2023A04J01514)the Lanzhou Chengguan District Science and Technology Plan Project(No.2022-rc-4)。
文摘Aqueous zinc ion batteries(ZIBs)feature high theoretical capacity,low cost,and high safety,but they suffer from moderate reversibility arising from electrolyte decomposition,Zn corrosion/passivation,and dendrite growth.To address this issue,an effective strategy is to construct a functional solid electrolyte interface(SEI)in situ.However,this is substantially challenging owing to the severe hydrogen evolution reaction(HER)and a lack of substances that can be decomposed to form SEI in the aqueous electrolytes.Herein,we propose the fabrication of a stable SEI in situ via a synergistic electrochemical reductionchemical precipitation approach.By chemically capturing the hydroxide ions(OH-)from HER,fatty acid methyl ester ethoxylate(FMEE),as an aqueous electrolyte additive,undergoes ester group hydrolysis following by a combination with Zn^(2+)to form insoluble fatty acid-zinc,enabling intelligent growth of a SEI on the Zn anode surface.As a result,the enhanced Zn anode exhibits a prolonged cycling life of up to 2700 h at 1 m A/cm^(2)and 1 m Ah/cm^(2).The Zn-V_(2)O_(5)full cell with the designed electrolyte demonstrates excellent rate capability and significantly improved cycling stability.This study presents a simple and practical strategy for in-situ formation of SEI in aqueous electrolytes,advancing the development of high-performance aqueous batteries.
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This work was supported by the National Natural Science Foundation of China(Grant Nos.82103472,82202480,and 52372252)the Hunan Natural Science Fund for Distinguished Young Scholar(2021JJ10064)the Program of Youth Talent Support for Hunan Province(2020RC3011).
文摘Biocompatible devices are widely employed in modernized lives and medical fields in the forms of wearable and implantable devices,raising higher requirements on the battery biocompatibility,high safety,low cost,and excellent electrochemical performance,which become the evaluation criteria toward developing feasible biocompatible batteries.Herein,through conducting the battery implantation tests and leakage scene simulations on New Zealand rabbits,zinc sulfate electrolyte is proved to exhibit higher biosecurity and turns out to be one of the ideal zinc salts for biocompatible zinc-ion batteries(ZIBs).Furthermore,in order to mitigate the notorious dendrite growth and hydrogen evolution in mildly acidic electrolyte as well as improve their operating stability,Sn hetero nucleus is introduced to stabilize the zinc anode,which not only facilitates the planar zinc deposition,but also contributes to higher hydrogen evolution overpotential.Finally,a long lifetime of 1500 h for the symmetrical cell,the specific capacity of 150 mAh g^(-1)under 0.5 A g^(-1)for the Zn-MnO_(2)battery and 212 mAh g^(-1)under 5 A g^(-1)for the Zn—NH4V4O10 battery are obtained.This work may provide unique perspectives on biocompatible ZIBs toward the biosecurity of their cell components.
基金financial support from the National Natural Science Foundation of China (52272261 and 52104300)。
文摘To tackle energy crisis and achieve sustainable development, aqueous rechargeable zinc ion batteries have gained widespread attention in large-scale energy storage for their low cost, high safety, high theoretical capacity, and environmental compatibility in recent years. However, zinc anode in aqueous zinc ion batteries is still facing several challenges such as dendrite growth and side reactions(e.g., hydrogen evolution), which cause poor reversibility and the failure of batteries. To address these issues, interfacial modification of Zn anodes has received great attention by tuning the interaction between the anode and the electrolyte. Herein, we present recent advances in the interfacial modification of zinc anode in this review. Besides, the challenges of reported approaches of interfacial modification are also discussed.Finally, we provide an outlook for the exploration of novel zinc anode for aqueous zinc ion batteries.We hope that this review will be helpful in designing and fabricating dendrite-free and hydrogenevolution-free Zn anodes and promoting the practical application of aqueous rechargeable zinc ion batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.51874110 and 51604089)Natural Science Foundation of Heilongjiang Province(YQ2021B004)Open Project of State Key Laboratory of Urban Water Resource and Environment(Grant No.QA202138).
文摘The last several years have witnessed the prosperous development of zinc-ion batteries(ZIBs),which are considered as a promising competitor of energy storage systems thanks to their low cost and high safety.However,the reversibility and availability of this system are blighted by problems such as uncontrollable dendritic growth,hydrogen evolution,and corrosion passivation on anode side.A functionally and structurally well-designed anode current collectors(CCs)is believed as a viable solution for those problems,with a lack of summarization according to its working mechanisms.Herein,this review focuses on the challenges of zinc anode and the mechanisms of modified anode CCs,which can be divided into zincophilic modification,structural design,and steering the preferred crystal facet orientation.The possible prospects and directions on zinc anode research and design are proposed at the end to hopefully promote the practical application of ZIBs.
基金the support from the National Natural Science Foundation of China(51972228 and 22109116)the TJU Nanoyang-Neware Joint Laboratory for Energy Innovation。
文摘Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given the limited operability of coating from polymer dispersions,it is imperative to develop simple aqueous-based strategies from monomers for versatile polymer coating.Herein,a Ti_(3)C_(2)Tx MXene-assisted approach is proposed to construct polymer coating on zinc metal surfaces directly from the aqueous solution of monomers in an ice bath.By combining a doctor-blading method with spontaneous polymerization of monomers on the substrates at room temperature,a uniform,adhesive,and versatile coating layer assisted by a small amount of MXene is produced in one step.Additionally,MXene nanosheets serve as nanofillers to further enhance the mechanical strength and ionic conductivity of the polymer coating.Benefiting from good film formation and improved interfacial contact,the coated zinc anode exhibits a long cycling lifespan of over 1900 h.The assembled full cells show excellent cycling stability with a high capacity retention of 85.0%at 16 A g^(-1)over 2600 cycles.This work provides a simple and efficient way to produce polymer coatings directly from monomers,which may give new insights into design multifunctional polymer coatings for various applications.
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.
基金National Natural Science Foundation of China(No.52002149)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515111202)the fellowship of China Postdoctoral Science Foundation(2020M683186)。
文摘Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.
基金financially supported by the Jiangsu Distinguished Professors Project (No.1711510024)the Funding for Scientific Research Startup of Jiangsu University (No.4111510015,19JDG044)+5 种基金the Jiangsu Provincial Program for High-Level Innovative and Entrepreneurial Talents Introductionthe National Natural Science Foundation of China (No.22008091)the Jiangsu Agriculture Science and Technology Innovation Fund (No.CX (21)1007)the Natural Science Foundation of Guangdong Province (2023A1515010894)the Open Project of Luzhou Key Laboratory of Fine Chemical Application Technology (HYJH-2302-A)the National Institute of Education,Singapore,under its Academic Research Fund (RI 1/21 EAH)。
文摘Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.In our investigation,we sought to mitigate these issues through the utilization of in situ zinc complex formation reactions to engineer hydrophobic protective layers on the zinc anode surface.These robust interfacial layers serve as effective barriers,isolating the zinc anode from the electrolyte and active water molecules and thereby preventing hydrogen evolution and the generation of undesirable byproducts.Additionally,the presence of numerous zincophilic sites within these protective layers facilitates uniform zinc deposition while concurrently inhibiting dendrite growth.Through comprehensive evaluation of functional anodes featuring diverse functional groups and alkyl chain lengths,we meticulously scrutinized the underlying mechanisms influencing performance variations.This analysis involved precise modulation of interfacial hydrophobicity,rapid Zn^(2+)ion transport,and ordered deposition of Zn^(2+)ions.Notably,the optimized anode,fabricated with octadecylphosphate(OPA),demonstrated exceptional performance characteristics.The Zn//Zn symmetric cell exhibited remarkable longevity,exceeding 4000 h under a current density of 2 mA cm^(-2)and a capacity density of 2 mA h cm^(-2),Furthermore,when integrated with a VOH cathode,the complete cell exhibited superior capacity retention compared to anodes modified with alternative organic molecules.
基金supported by the National Natural Science Foundation of China(Grant Nos.52072285,52127816,51872218)the National Key Research and Development Program of China(Grant No.2020YFA0715000)the Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(Grant No.XHT2020-003).
文摘Aqueous zinc ion batteries have been considered as the prominent candidate in the next-generation batteries for its low cost,safety and high theoretical capacity.Nonetheless,formation of zinc dendrites and side reactions at the electrode/electrolyte interface during the zinc plating/stripping process affect the cycling reversibility of the zinc anode.Regulation of the zinc plating/stripping process and realizing a highly reversible zinc anode is a great challenge.Herein,we applied a simple and effective approach of controlled-current zinc pre-deposition at copper mesh.At the current density of 40 mA cm^(-2),where the electron/ion transfers are both continuous and balanced,the Zn@CM-40 electrode with the(002)crystal plane orientation and the compactly aligned platelet morphology was successfully obtained.Compared with the zinc foil,the Zn@CM-40 exhibits greatly enhanced reversibility in the repeated plating/stripping(850 h at 1 mA cm^(-2))for the symmetric battery test.A series of characterization techniques including electrochemical analyses,XRD,SEM and optical microscopy observation,were used to demonstrate the correlation between the structure of pre-deposited zinc layer and the cycling stability.The COSMOL Multiphysics modeling demonstrates a more uniform electric field distribution in the Zn@CM than the zinc foil due to the aligned platelet morphology.Furthermore,the significant improvement is also achieved in a Zn||MnO_(2)full battery with a high capacity-retention(87%vs 47.8%).This study demonstrates that controlled-current electrodeposition represents an important strategy to regulate the crystal plane orientation and the morphology of the pre-deposited zinc layer,hence leading to the highly reversible and dendrite-free zinc anode for high-performance zinc ion batteries.
基金supported from the National Research Council of Thailand(NRCT):NRCT-RSA63001-19Second Century Fund(C2F),Chulalongkorn University.
文摘The uncontrollable dendrites growth and intricately water-induced side reactions occurred on zinc anode leads to safety issues and poor electrochemical kinetics,which largely limit the widespread application of zinc-ion batteries(ZIBs).Herein,ethylenediaminetetraacetic acid disodium salt(EDTA-2Na)is utilized as an electrolyte additive to strengthen the reversibility and cycling stability of zinc anode.Experimental results and theoretical calculation demonstrate that the EDTA-2Na presents a much stronger coordination with Zn^(2+)when comparing with H_(2)O molecular,implying the EDTA-2Na is capable to enter the solvation shell of[Zn(OH_(2))_(6)]^(2+)and coordinate with Zn^(2+)ions,thus achieving a flat and smooth zinc deposition with less by-products(Zn_(4)SO_(4)(OH)6·xH_(2)O and H_(2)).Consequently,the zinc symmetric battery with EDTA-2Na additive delivers an excellent cycling stability up to 1800 h under current density of 1 mA cm^(-2),and the hydrogen evolution reaction(HER),corrosion,by-product issues are significantly inhibited.Moreover,the rate performance and stability of coin-type and pouch-type Zn||MnO2/graphite batteries are significantly boosted via EDTA-2Na additive(248 mAh g^(-1)at 0.1 A g^(-1),81.3%after 1000 cycles at a A g^(-1)).This kind of electrolyte additive with chelation and desolvation functions shed lights on strategies of improving zinc anode stability for further application of ZIBs.
基金supported by financial support from the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(NRF-2020R1A3B2079803 and NRF2019K1A3A1A21032033),Republic of Korea。
文摘Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution reaction.Herein,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full batteries.The as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 cycles.Moreover,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 cycles.The high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.
基金financially supported by the National Natural Science Foundation of China(22168019 and 52074141)the Major Science and Technology Projects in Yunnan Province(202202AB080014)+1 种基金The authors are grateful to the National Natural Science Foundation of Chinathe Major Science and Technology Projects in Yunnan Province for their support.
文摘Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.
基金supported by the grants from the Research Grants Council of the Hong Kong Special Administrative Region,China(Project No.C5031-20)the Guangdong Major Project of Basic and Applied Basic Research(2023B0303000002).
文摘Zinc metal anodes are gaining popularity in aqueous electrochemical energy storage systems for their high safety,cost-effectiveness,and high capacity.However,the service life of zinc metal anodes is severely constrained by critical challenges,including dendrites,water-induced hydrogen evolution,and passivation.In this study,a protective two-dimensional metal–organic framework interphase is in situ constructed on the zinc anode surface with a novel gel vapor deposition method.The ultrathin interphase layer(~1μm)is made of layer-stacking 2D nanosheets with angstrom-level pores of around 2.1Å,which serves as an ion sieve to reject large solvent–ion pairs while homogenizes the transport of partially desolvated zinc ions,contributing to a uniform and highly reversible zinc deposition.With the shielding of the interphase layer,an ultra-stable zinc plating/stripping is achieved in symmetric cells with cycling over 1000 h at 0.5 mA cm−2 and~700 h at 1 mA cm^(−2),far exceeding that of the bare zinc anodes(250 and 70 h).Furthermore,as a proof-of-concept demonstration,the full cell paired with MnO_(2) cathode demonstrates improved rate performances and stable cycling(1200 cycles at 1 A g−1).This work provides fresh insights into interphase design to promote the performance of zinc metal anodes.
基金the financial support from the Australian Research Council,Centre for Materials Science,Queensland University of Technologythe Supported by the Fundamental Research Funds for the Central Universities。
文摘Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.
