Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hamp...Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hampered by the instability of both the anode-electrolyte interface and the cathode-electrolyte interface.The use of sodium gluconate(SG),an organic sodium salt with multiple hydroxyl groups,as an electrolyte additive is suggested.Experimental and theoretical analyses demonstrate that Na^(+)from SG can intercalate and deintercalate within the associated V_(2)O_(5) cathode during in situ electrochemical processes.This action supports the layered structure of V_(2)O_(5),prevents structural collapse and phase transitions,and enhances Zn^(2+)diffusion kinetics.Additionally,the gluconate anion disrupts the original Zn^(2+)solvation structure,mitigates water-induced side reactions,and suppresses Zn dendrite growth.The synchronous regulation of both the V_(2)O_(5) cathode and Zn anode by the SG additive leads to considerable performance improvements.Zn‖Zn symmetric batteries demonstrate a cycle life exceeding 2800 h at 0.5 mA cm^(-2)and 1 mAh cm^(-2).In Zn‖V_(2)O_(5) full batteries,a high specific capacity of 288.92 mAh g^(-1)and capacity retention of 82.29%are maintained over 1000 cycles at a current density of 2 A g^(-1).This multifunctional additive strategy offers a new pathway for the practical application of AZIBs.展开更多
Aqueous Zinc-metal batteries(AZBs)hold great promise for energy storage applications,yet their practical deployment is hindered by challenges such as dendrite formation and parasitic side reactions at the Zn anode.Her...Aqueous Zinc-metal batteries(AZBs)hold great promise for energy storage applications,yet their practical deployment is hindered by challenges such as dendrite formation and parasitic side reactions at the Zn anode.Herein,we developed a three-dimensional Cu-coated flexible host via an electroless plating strategy on cotton cloth(Cu@CT).This design effectively homogenizes the local current density,spatially regulates Zn-ion flux,and accommodates substantial volume changes during cycling.Additionally,the zincophilic Cu coating facilitates Zn nucleation and deposition by forming Cu-Zn alloys,which reduce the Zn nucleation overpotential and promote uniform Zn plating.As a result,the Cu@CT based anode exhibits highly reversible Zn plating/stripping behavior with an average Coulombic efficiency of 99.58%over 800 cycles,accompanied by low polarization and dendrite-free behavior.Moreover,the Zn-I2 full cell demonstrates excellent rate capability,delivering a discharge capacity of 114 mA h g^(-1) at 10 A g^(-1),along with stable long-term cycling performance over 950 cycles.The electroless plating strategy may represent a promising pathway for advancing high-performance AZBs.展开更多
H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an elec...H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.展开更多
Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was...Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was introduced into aqueous electrolyte to modulate the interfacial electrochemistry of Zn anode.In AZMBs,the positively charged side of Tyr can be well adsorbed on the surface of Zn anode to form a water-poor layer,and the exposed carboxylate side can be easily coordinated with Zn^(2+),favoring inducing uniform plating of Zn^(2+)and inhibiting the occurrence of water-induced side reactions.These in turn enable the achievement of highly stable Zn anode.Accordingly,the Zn anodes achieve outstanding cyclic stability(3000 h at 2 mA cm^(-2),2 mA h cm^(-2)and 1300 h at 5 mA cm^(-2),5 mA h cm^(-2)),high average Coulombic efficiency(99.4%over 3200 cycles),and high depth of discharge(80%for 500 h).Besides,the assembled Zn‖NaV_(3)O_(8)·1.5H_(2)O full cells deliver remarkable capacity retention and ultra-long lifetime(61.8%over 6650 cycles at 5 A g^(-1))and enhanced rate capability(169 mA h g^(-1)at 5 A g^(-1)).The work may promote the design and deep understanding of electrolyte additives with high molecular polarity for high-performance AZMBs.展开更多
Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic react...Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.展开更多
Rechargeable aqueous Zn-ion batteries(ZIBs)have emerged as a promising new energy storage technology,characterized by their low cost,high safety,environmental friendliness,and the abundant availability of Zn resources...Rechargeable aqueous Zn-ion batteries(ZIBs)have emerged as a promising new energy storage technology,characterized by their low cost,high safety,environmental friendliness,and the abundant availability of Zn resources.However,several challenges remain with their use,such as zinc dendrite formation,corrosion,passivation,and hydrogen evolution reaction(HER)on the zinc anodesurface,leading to a short overall battery life.In this paper,a zinc anode-coating method with silica-fly ash composite(FAS)has been developed.This modified Zn anode(5FAS@Zn)demonstrates remarkable improvements in the performance and stability of ZIBs by effectively decreasing zinc nucleation overpotential and minimizing charge transfer resistance while facilitating stable Zn plating and stripping as well as achieving even zinc deposition.The remarkable cycling lifespan of the 5FAS@Znll5FAS@Zn symmetrical cell is 1800 h at 0.5 mA cm^(-2)and 1500 h at1 mA cm^(-2).The 5FAS@ZnllCu half-cell outperforms pure Zn batteries with a high and consistent Coulombic efficiency(CE)of 99.8%over 800 cycles at 1 mA cm^(-2).Furthermore,the full cell of 5FAS@ZnllV_(2)O_(5)exhibits notable improvements in cycling performance.This research provides a scalable and sustainable method to extend the life of zinc anodes and has significant implications for the large-scale deployment of zinc-ion batteries.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.展开更多
Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the ...Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.展开更多
Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte...Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte plays a crucial role in these processes,significantly impacting the stability and reversibility of Zn^(2+)deposition.Therefore,pH-buffer tris(hydroxymethyl)amino methane(tris)is chosen as a versatile electrolyte additive to address these issues.Tris can buffer electrolyte pH at Zn/electrolyte interface by protonated/deprotonated nature of amino group,optimize the coordination environment of zinc solvate ions by its strong interaction with zinc ions,and simultaneously create an in-situ stable solid electrolyte interface membrane on the zinc anode surface.These synergistic effects effectively restrain dendrite formation and side reactions,resulting in a highly stable and reversible Zn anode,thereby enhancing the electrochemical performance of AZIBs.The Zn||Zn battery with 0.15 wt%tris additives maintains stable cycling for 1500 h at 4 mA·cm^(−2) and 1120 h at 10 mA·cm^(−2).Furthermore,the Coulombic efficiency reaches~99.2%at 4 mA·cm^(−2)@1 mAh·cm^(−2).The Zn||NVO full batteries also demonstrated a stable specific capacity and exceptional capacity retention.展开更多
Aqueous zinc-ion batteries(ZIBs) combine the benefits of metallic Zn anodes with those of aqueous electrolytes and are well suited for large-scale energy storage because of their inherent high safety, cost-effectivene...Aqueous zinc-ion batteries(ZIBs) combine the benefits of metallic Zn anodes with those of aqueous electrolytes and are well suited for large-scale energy storage because of their inherent high safety, cost-effectiveness, and eco-friendliness. Currently, the practical application of such batteries is hindered by the poor cycling performance of Zn anodes due to uncontrolled dendrite formation and severe side reactions, although recent reports suggest that these problems can be mitigated through the modification of Zn anodes with metal-based materials.Given that the mechanisms of improving Zn deposition and the structural evolution of metal-based materials have not been systematically reviewed, we herein systematically overview the metal-based materials used to stabilize Zn anodes, starting with a brief summary of the anode working mechanism and the challenges faced by stabilized Zn anodes. Subsequently, the design principles of Zn anodes stabilized by metal-based materials and the related recent progress are reviewed, and the key challenges and perspectives for the future development of such Zn anodes are proposed.展开更多
With the growing energy demand associated with high safety and low-cost requirement,aqueous zinc-ion batteries(AZIBs)have been considered as one of the most promising next-generation batteries.However,some key issues,...With the growing energy demand associated with high safety and low-cost requirement,aqueous zinc-ion batteries(AZIBs)have been considered as one of the most promising next-generation batteries.However,some key issues,such as uncontrollable dendrites growth,severe corrosion,hydrogen evolution and side reactions of Zn anodes during charge/discharge process,have hindered its pragmatic applications.Two-dimensional(2D)materials hold advantages of unique physical and chemical properties,large surface areas and abundant active sites,which have been successfully used to overcome the above shortcomings of Zn anodes in recent years.In this review,the issues and challenges of Zn anodes are outlined.Then,the state-of-the-art progress on Zn anodes modification based on 2D materials such as graphene,2D metal carbides and nitrides(MXenes),2D metal-organic frameworks(MOFs),2D covalent organic frameworks(COFs),2D transition metal compounds and other 2D materials is discussed in detail.Finally,the perspectives of employing 2D materials in highly reversible Zn anodes are summarized and discussed.展开更多
Aqueous Zn^(2+)-ion batteries(AZIBs),recognized for their high security,reliability,and cost efficiency,have garnered considerable attention.However,the prevalent issues of dendrite growth and parasitic reactions at t...Aqueous Zn^(2+)-ion batteries(AZIBs),recognized for their high security,reliability,and cost efficiency,have garnered considerable attention.However,the prevalent issues of dendrite growth and parasitic reactions at the Zn electrode interface significantly impede their practical application.In this study,we introduced a ubiquitous biomolecule of phenylalanine(Phe)into the electrolyte as a multifunctional additive to improve the reversibility of the Zn anode.Leveraging its exceptional nucleophilic characteristics,Phe molecules tend to coordinate with Zn^(2+)ions for optimizing the solvation environment.Simultaneously,the distinctive lipophilicity of aromatic amino acids empowers Phe with a higher adsorption energy,enabling the construction of a multifunctional protective interphase.The hydrophobic benzene ring ligands act as cleaners for repelling H_(2)O molecules,while the hydrophilic hydroxyl and carboxyl groups attract Zn^(2+)ions for homogenizing Zn^(2+)flux.Moreover,the preferential reduction of Phe molecules prior to H_(2)O facilitates the in situ formation of an organic-inorganic hybrid solid electrolyte interphase,enhancing the interfacial stability of the Zn anode.Consequently,Zn||Zn cells display improved reversibility,achieving an extended cycle life of 5250 h.Additionally,Zn||LMO full cells exhibit enhanced cyclability of retaining 77.3%capacity after 300 cycles,demonstrating substantial potential in advancing the commercialization of AZIBs.展开更多
Aqueous Zn-ion batteries(AZIBs) have emerged as potential candidates for Li-ion batteries due to their intrinsic safety and high capacity.However,metallic Zn anodes encounter dendrite growth and water-induced corrosio...Aqueous Zn-ion batteries(AZIBs) have emerged as potential candidates for Li-ion batteries due to their intrinsic safety and high capacity.However,metallic Zn anodes encounter dendrite growth and water-induced corrosion,rendering poor stability and severe irreversibility at the electrode/electrolyte interface during cycling.To stabilize the Zn anode,we report a low-cost and effective nonionic surfactant,Tween-20 polymer,as an electrolyte additive for AZIBs.For Tween-20,sequential oxyethylene groups tended to be preferentially adsorbed on the Zn electrode to form a shielding layer for regulating uniform Zn nucleation.Moreover,the hydrophobic hendecyl chains prevented H_(2)O-induced corrosion on the Zn anode surface.Benefiting from the desired functional groups,when only trace amounts of Tween-20(0.050 g·L^(-1)) were used,the Zn anode displayed good cycling stability over 2170 h at10 mA·cm^(-2) and a high average Coulombic efficiency of98.94% over 1000 cycles.The Tween-20 polymer can also be effectively employed in MnO_(2)/Zn full batteries.Considering their toxicity,price and amount of usage,these surfactant additives provide a promising strategy for realizing the stability and reversibility of high-performance Zn anodes.展开更多
The uncontrollable growth of Zn dendrites accompanied by side reactions severely impedes the industrialized process of zinc ion electrochemical energy storage devices.Herein,we propose a practical metalorganic complex...The uncontrollable growth of Zn dendrites accompanied by side reactions severely impedes the industrialized process of zinc ion electrochemical energy storage devices.Herein,we propose a practical metalorganic complex interface layer to manipulate the zinc ion flux and electric field intensity,enabling highly homogeneous zinc electrodeposition.The zinc-terephthalic acid complex(ZnPTA)with lower adsorption energy for zinc ion(-1.3 eV)builds a zincophilic interface favoring the ordered nucleation and growth of Zn.Moreover,the ZnPTA layer can serve as physical barrier to protect the newly deposited Zn from corrosion in the aqueous electrolyte.The modified Zn anode with the ZnPTA layer(ZnPTA@Zn)demonstrates excellent cycling stability more than 3000 h at 1 mA/cm^(2).Besides,the zinc-ion battery and zinc-ion hybrid capacitor using the ZnPTA@Zn electrode deliver outstanding cycle performance(up to 5500 cycles with high residual capacity ratio of 77.9%).This work provides a promising metal-organic complex interface design on enhancing the performance of Zn metal anode.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising high-efficiency energy storage system due to the high energy density,low-cost and environmental friendliness.However,the practical application of AZIBs is s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising high-efficiency energy storage system due to the high energy density,low-cost and environmental friendliness.However,the practical application of AZIBs is severely restricted by the challenges faced by the Zn anode,which include uncontrollable dendrite growth,corrosion and hydrogen evolution reaction.Herein,a simple and convenient physical vapor deposition(PVD)method is reported for fabricating uniform graphite as a protection layer on the surface of Zn anode.The high conductivity graphite layer on Zn anode(denoted as Zn@C)not only benefits the uniform distribution of the electric field,but also provides numerous Zn nucleation sites to regulate and navigate Zn-ion stripping/plating behaviors.Additionally,the graphite layer with a poor catalytic activity endows the Zn@C anode with a highly suppressed hydrogen evolution.Consequently,a hydrogen and dendrite free anode is achieved with artificial anticatalytic carbon layer on Zn anode,exhibiting a high reversibility and excellent cycling stability over 2600 h at the current density of 5 mA·cm^(-2)with a capacity of 2.5 mAh·cm^(-2)and longtime cycling stability for assembled full cells.This work strategically designs the properties of the artificial interface layer to effectively address various challenges simultaneously,which presents insights for the future development of high-performance rechargeable AZIBs.展开更多
Zn metal anodes are usually subject to grave dendrite growth during platting/stripping,which dramatically curtails the lifespan of aqueous Zn-ion batteries and capacitors.To address above problems,in our work,a novel ...Zn metal anodes are usually subject to grave dendrite growth during platting/stripping,which dramatically curtails the lifespan of aqueous Zn-ion batteries and capacitors.To address above problems,in our work,a novel phosphorus-functionalized multichannel carbon interlayer was designed and covered on Zn anodes.The results demonstrated that the multichannel structure combined with the three-dimensional meshy skeleton can provide more sufficient space for Zn deposition,thereby effectively inhibiting the growth of zinc dendrites.Meanwhile,theoretical calculations also confirmed that the P-C and P=O functional groups from phosphorus-functionalized multichannel carbon interlayer have the decisive influence in reducing the zinc nucleation potential and depositing uniformly zinc.Concretely,the symmetrical battery assembled with phosphorus-functionalized multichannel carbon interlayer-covered Zn anodes possessed a long lifetime of 3300 h at 2 mA cm^(-2)with 1 mAh cm^(-2).Furthermore,the full cell with activated carbon cathodes exhibited a high specific capacity of 80.5 mAh g^(-1)and outstanding cycling stability without capacity decay after 15000 cycles at a high current density of 5 A g^(-1).The superior electrochemical performance exceeded that of most reported papers.Consequently,our synthesized zincophilic interlayer with the unique structure has superior prospects for application in stabilizing zinc anodes and prolonging the lifespan of batteries.展开更多
The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based...The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.展开更多
Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn den...Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.展开更多
Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes tha...Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes that originates from dendrite growth,surface passivation and corrosion,severely hinders the further development of ZBs.To tackle these issues,here we report a Janus separator based on a Zn-ion conductive metal-organic framework(MOF)and reduced graphene oxide(rGO),which is able to regulate uniform Zn2+flux and electron conduction simultaneously during battery operation.Facilitated by the MOF/rGO bifunctional interlayers,the Zn anodes demonstrate stable plating/stripping behavior(over 500 h at 1 mA cm^(−2)),high Coulombic efficiency(99.2%at 2 mA cm^(−2) after 100 cycles)and reduced redox barrier.Moreover,it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface.Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells,which deliver nearly 100%capacity retention after 2000 cycles at 4 A g^(−1) and high power density over 10 kW kg^(−1).This work provides a feasible route to the high-performance Zn anodes for ZBs.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
基金supported by the Battery Energy Storage Testing Center of Chongqing through their provision of testing support and technical assistance。
文摘Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hampered by the instability of both the anode-electrolyte interface and the cathode-electrolyte interface.The use of sodium gluconate(SG),an organic sodium salt with multiple hydroxyl groups,as an electrolyte additive is suggested.Experimental and theoretical analyses demonstrate that Na^(+)from SG can intercalate and deintercalate within the associated V_(2)O_(5) cathode during in situ electrochemical processes.This action supports the layered structure of V_(2)O_(5),prevents structural collapse and phase transitions,and enhances Zn^(2+)diffusion kinetics.Additionally,the gluconate anion disrupts the original Zn^(2+)solvation structure,mitigates water-induced side reactions,and suppresses Zn dendrite growth.The synchronous regulation of both the V_(2)O_(5) cathode and Zn anode by the SG additive leads to considerable performance improvements.Zn‖Zn symmetric batteries demonstrate a cycle life exceeding 2800 h at 0.5 mA cm^(-2)and 1 mAh cm^(-2).In Zn‖V_(2)O_(5) full batteries,a high specific capacity of 288.92 mAh g^(-1)and capacity retention of 82.29%are maintained over 1000 cycles at a current density of 2 A g^(-1).This multifunctional additive strategy offers a new pathway for the practical application of AZIBs.
基金supported by the National Natural Science Foundation of China(52301285,52173091,and 22208331)Wuhan Science and Technology Bureau(2024040801020319)Department of Science and Technology of Hubei Province(2021CSA076).
文摘Aqueous Zinc-metal batteries(AZBs)hold great promise for energy storage applications,yet their practical deployment is hindered by challenges such as dendrite formation and parasitic side reactions at the Zn anode.Herein,we developed a three-dimensional Cu-coated flexible host via an electroless plating strategy on cotton cloth(Cu@CT).This design effectively homogenizes the local current density,spatially regulates Zn-ion flux,and accommodates substantial volume changes during cycling.Additionally,the zincophilic Cu coating facilitates Zn nucleation and deposition by forming Cu-Zn alloys,which reduce the Zn nucleation overpotential and promote uniform Zn plating.As a result,the Cu@CT based anode exhibits highly reversible Zn plating/stripping behavior with an average Coulombic efficiency of 99.58%over 800 cycles,accompanied by low polarization and dendrite-free behavior.Moreover,the Zn-I2 full cell demonstrates excellent rate capability,delivering a discharge capacity of 114 mA h g^(-1) at 10 A g^(-1),along with stable long-term cycling performance over 950 cycles.The electroless plating strategy may represent a promising pathway for advancing high-performance AZBs.
基金supported by the National Natural Science Foundation of China(22479031,22162004)the Natural Science Foundation of Guangxi(2022JJD120011).
文摘H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003).
文摘Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was introduced into aqueous electrolyte to modulate the interfacial electrochemistry of Zn anode.In AZMBs,the positively charged side of Tyr can be well adsorbed on the surface of Zn anode to form a water-poor layer,and the exposed carboxylate side can be easily coordinated with Zn^(2+),favoring inducing uniform plating of Zn^(2+)and inhibiting the occurrence of water-induced side reactions.These in turn enable the achievement of highly stable Zn anode.Accordingly,the Zn anodes achieve outstanding cyclic stability(3000 h at 2 mA cm^(-2),2 mA h cm^(-2)and 1300 h at 5 mA cm^(-2),5 mA h cm^(-2)),high average Coulombic efficiency(99.4%over 3200 cycles),and high depth of discharge(80%for 500 h).Besides,the assembled Zn‖NaV_(3)O_(8)·1.5H_(2)O full cells deliver remarkable capacity retention and ultra-long lifetime(61.8%over 6650 cycles at 5 A g^(-1))and enhanced rate capability(169 mA h g^(-1)at 5 A g^(-1)).The work may promote the design and deep understanding of electrolyte additives with high molecular polarity for high-performance AZMBs.
基金supported by Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(No.2021JJLH0069)the Project of Sanya Yazhou Bay Science and Technology City(No.SCKJ-JYRC-2023-55)Hainan Provincial Natural Science Foundation of China(No.522CXTD516).
文摘Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.
基金financially supported by the Thailand Science Research and Innovation Fund Chulalongkorn Universitythe National Research Council of Thailand(No.N11A670659)the National Natural Science Foundation of China(Nos.52125405 and U22A20108)
文摘Rechargeable aqueous Zn-ion batteries(ZIBs)have emerged as a promising new energy storage technology,characterized by their low cost,high safety,environmental friendliness,and the abundant availability of Zn resources.However,several challenges remain with their use,such as zinc dendrite formation,corrosion,passivation,and hydrogen evolution reaction(HER)on the zinc anodesurface,leading to a short overall battery life.In this paper,a zinc anode-coating method with silica-fly ash composite(FAS)has been developed.This modified Zn anode(5FAS@Zn)demonstrates remarkable improvements in the performance and stability of ZIBs by effectively decreasing zinc nucleation overpotential and minimizing charge transfer resistance while facilitating stable Zn plating and stripping as well as achieving even zinc deposition.The remarkable cycling lifespan of the 5FAS@Znll5FAS@Zn symmetrical cell is 1800 h at 0.5 mA cm^(-2)and 1500 h at1 mA cm^(-2).The 5FAS@ZnllCu half-cell outperforms pure Zn batteries with a high and consistent Coulombic efficiency(CE)of 99.8%over 800 cycles at 1 mA cm^(-2).Furthermore,the full cell of 5FAS@ZnllV_(2)O_(5)exhibits notable improvements in cycling performance.This research provides a scalable and sustainable method to extend the life of zinc anodes and has significant implications for the large-scale deployment of zinc-ion batteries.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.
基金National Natural Science Foundation of China (52301273, 52072411)Science and Technology Innovation Program of Hunan Province (2024RC3222)+3 种基金Key project of scientific research project of Hunan Provincial Department of Education (22A0479)China Postdoctoral Science Foundation (2024M753668)Central South University Innovation-Driven Research Programme (2023CXQD038)Hunan Provincial Postgraduate Research Innovation Programme(CX20240970)。
文摘Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.
基金supported by the Fund of Xuzhou Science and Technology Key R&D Program(Social Development)Project(No.KC22289)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX22_2783).
文摘Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte plays a crucial role in these processes,significantly impacting the stability and reversibility of Zn^(2+)deposition.Therefore,pH-buffer tris(hydroxymethyl)amino methane(tris)is chosen as a versatile electrolyte additive to address these issues.Tris can buffer electrolyte pH at Zn/electrolyte interface by protonated/deprotonated nature of amino group,optimize the coordination environment of zinc solvate ions by its strong interaction with zinc ions,and simultaneously create an in-situ stable solid electrolyte interface membrane on the zinc anode surface.These synergistic effects effectively restrain dendrite formation and side reactions,resulting in a highly stable and reversible Zn anode,thereby enhancing the electrochemical performance of AZIBs.The Zn||Zn battery with 0.15 wt%tris additives maintains stable cycling for 1500 h at 4 mA·cm^(−2) and 1120 h at 10 mA·cm^(−2).Furthermore,the Coulombic efficiency reaches~99.2%at 4 mA·cm^(−2)@1 mAh·cm^(−2).The Zn||NVO full batteries also demonstrated a stable specific capacity and exceptional capacity retention.
基金financially supported by the National Natural Science Foundation of China (No.62101296)the Natural Science Foundation of Shaanxi Province (No.2021JQ-760 and 2021JQ-756)。
文摘Aqueous zinc-ion batteries(ZIBs) combine the benefits of metallic Zn anodes with those of aqueous electrolytes and are well suited for large-scale energy storage because of their inherent high safety, cost-effectiveness, and eco-friendliness. Currently, the practical application of such batteries is hindered by the poor cycling performance of Zn anodes due to uncontrolled dendrite formation and severe side reactions, although recent reports suggest that these problems can be mitigated through the modification of Zn anodes with metal-based materials.Given that the mechanisms of improving Zn deposition and the structural evolution of metal-based materials have not been systematically reviewed, we herein systematically overview the metal-based materials used to stabilize Zn anodes, starting with a brief summary of the anode working mechanism and the challenges faced by stabilized Zn anodes. Subsequently, the design principles of Zn anodes stabilized by metal-based materials and the related recent progress are reviewed, and the key challenges and perspectives for the future development of such Zn anodes are proposed.
基金financially supported by the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.RF-B-2020004)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2020R01002)+2 种基金the National Key Research and Development Project of China(No.2022YFE0113800)the National Natural Science Foundation of China(Nos.51972286,21905246 and 22005268)the Natural Science Foundation of Zhejiang Province(Nos.LR19E020003,LZ21E020003,LQ21E020004 and LQ20B010011)。
文摘With the growing energy demand associated with high safety and low-cost requirement,aqueous zinc-ion batteries(AZIBs)have been considered as one of the most promising next-generation batteries.However,some key issues,such as uncontrollable dendrites growth,severe corrosion,hydrogen evolution and side reactions of Zn anodes during charge/discharge process,have hindered its pragmatic applications.Two-dimensional(2D)materials hold advantages of unique physical and chemical properties,large surface areas and abundant active sites,which have been successfully used to overcome the above shortcomings of Zn anodes in recent years.In this review,the issues and challenges of Zn anodes are outlined.Then,the state-of-the-art progress on Zn anodes modification based on 2D materials such as graphene,2D metal carbides and nitrides(MXenes),2D metal-organic frameworks(MOFs),2D covalent organic frameworks(COFs),2D transition metal compounds and other 2D materials is discussed in detail.Finally,the perspectives of employing 2D materials in highly reversible Zn anodes are summarized and discussed.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U2130204)the National Natural Science Foundation of China(52002022)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(YESS20200364)the Beijing Outstanding Young Scientists Program(BJJWZYJH01201910007023).
文摘Aqueous Zn^(2+)-ion batteries(AZIBs),recognized for their high security,reliability,and cost efficiency,have garnered considerable attention.However,the prevalent issues of dendrite growth and parasitic reactions at the Zn electrode interface significantly impede their practical application.In this study,we introduced a ubiquitous biomolecule of phenylalanine(Phe)into the electrolyte as a multifunctional additive to improve the reversibility of the Zn anode.Leveraging its exceptional nucleophilic characteristics,Phe molecules tend to coordinate with Zn^(2+)ions for optimizing the solvation environment.Simultaneously,the distinctive lipophilicity of aromatic amino acids empowers Phe with a higher adsorption energy,enabling the construction of a multifunctional protective interphase.The hydrophobic benzene ring ligands act as cleaners for repelling H_(2)O molecules,while the hydrophilic hydroxyl and carboxyl groups attract Zn^(2+)ions for homogenizing Zn^(2+)flux.Moreover,the preferential reduction of Phe molecules prior to H_(2)O facilitates the in situ formation of an organic-inorganic hybrid solid electrolyte interphase,enhancing the interfacial stability of the Zn anode.Consequently,Zn||Zn cells display improved reversibility,achieving an extended cycle life of 5250 h.Additionally,Zn||LMO full cells exhibit enhanced cyclability of retaining 77.3%capacity after 300 cycles,demonstrating substantial potential in advancing the commercialization of AZIBs.
基金financially supported by the National Natural Science Foundation of China (Nos.22102157 and U1910208)the Natural Science Foundation of Shanxi Province of China (Nos.20210302124097 and 20210302124663)+2 种基金the Opening Foundation of Shanxi Provincial Key Laboratory for HighPerformance Battery Materials and Devices (No.2022HPBMD02002)the Graduate Student Innovation Program of North University of China (No.20221871)the Natural Science Foundation of Hubei Province of China (No.2022CFB577)。
文摘Aqueous Zn-ion batteries(AZIBs) have emerged as potential candidates for Li-ion batteries due to their intrinsic safety and high capacity.However,metallic Zn anodes encounter dendrite growth and water-induced corrosion,rendering poor stability and severe irreversibility at the electrode/electrolyte interface during cycling.To stabilize the Zn anode,we report a low-cost and effective nonionic surfactant,Tween-20 polymer,as an electrolyte additive for AZIBs.For Tween-20,sequential oxyethylene groups tended to be preferentially adsorbed on the Zn electrode to form a shielding layer for regulating uniform Zn nucleation.Moreover,the hydrophobic hendecyl chains prevented H_(2)O-induced corrosion on the Zn anode surface.Benefiting from the desired functional groups,when only trace amounts of Tween-20(0.050 g·L^(-1)) were used,the Zn anode displayed good cycling stability over 2170 h at10 mA·cm^(-2) and a high average Coulombic efficiency of98.94% over 1000 cycles.The Tween-20 polymer can also be effectively employed in MnO_(2)/Zn full batteries.Considering their toxicity,price and amount of usage,these surfactant additives provide a promising strategy for realizing the stability and reversibility of high-performance Zn anodes.
基金supported by the Fundamental Research Funds for the Central Universities,China。
文摘The uncontrollable growth of Zn dendrites accompanied by side reactions severely impedes the industrialized process of zinc ion electrochemical energy storage devices.Herein,we propose a practical metalorganic complex interface layer to manipulate the zinc ion flux and electric field intensity,enabling highly homogeneous zinc electrodeposition.The zinc-terephthalic acid complex(ZnPTA)with lower adsorption energy for zinc ion(-1.3 eV)builds a zincophilic interface favoring the ordered nucleation and growth of Zn.Moreover,the ZnPTA layer can serve as physical barrier to protect the newly deposited Zn from corrosion in the aqueous electrolyte.The modified Zn anode with the ZnPTA layer(ZnPTA@Zn)demonstrates excellent cycling stability more than 3000 h at 1 mA/cm^(2).Besides,the zinc-ion battery and zinc-ion hybrid capacitor using the ZnPTA@Zn electrode deliver outstanding cycle performance(up to 5500 cycles with high residual capacity ratio of 77.9%).This work provides a promising metal-organic complex interface design on enhancing the performance of Zn metal anode.
基金financially supported by the National Natural Science Foundation of China(No.22222902)Natural Science Foundation of Jiangsu Province(No.BK20200047)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising high-efficiency energy storage system due to the high energy density,low-cost and environmental friendliness.However,the practical application of AZIBs is severely restricted by the challenges faced by the Zn anode,which include uncontrollable dendrite growth,corrosion and hydrogen evolution reaction.Herein,a simple and convenient physical vapor deposition(PVD)method is reported for fabricating uniform graphite as a protection layer on the surface of Zn anode.The high conductivity graphite layer on Zn anode(denoted as Zn@C)not only benefits the uniform distribution of the electric field,but also provides numerous Zn nucleation sites to regulate and navigate Zn-ion stripping/plating behaviors.Additionally,the graphite layer with a poor catalytic activity endows the Zn@C anode with a highly suppressed hydrogen evolution.Consequently,a hydrogen and dendrite free anode is achieved with artificial anticatalytic carbon layer on Zn anode,exhibiting a high reversibility and excellent cycling stability over 2600 h at the current density of 5 mA·cm^(-2)with a capacity of 2.5 mAh·cm^(-2)and longtime cycling stability for assembled full cells.This work strategically designs the properties of the artificial interface layer to effectively address various challenges simultaneously,which presents insights for the future development of high-performance rechargeable AZIBs.
基金supported by the National Natural Science Foundation(NSFC)of China(22179094)the research funding provided by Cangzhou Institute of Tiangong University(Grant No.TGCYY-Z-0202)
文摘Zn metal anodes are usually subject to grave dendrite growth during platting/stripping,which dramatically curtails the lifespan of aqueous Zn-ion batteries and capacitors.To address above problems,in our work,a novel phosphorus-functionalized multichannel carbon interlayer was designed and covered on Zn anodes.The results demonstrated that the multichannel structure combined with the three-dimensional meshy skeleton can provide more sufficient space for Zn deposition,thereby effectively inhibiting the growth of zinc dendrites.Meanwhile,theoretical calculations also confirmed that the P-C and P=O functional groups from phosphorus-functionalized multichannel carbon interlayer have the decisive influence in reducing the zinc nucleation potential and depositing uniformly zinc.Concretely,the symmetrical battery assembled with phosphorus-functionalized multichannel carbon interlayer-covered Zn anodes possessed a long lifetime of 3300 h at 2 mA cm^(-2)with 1 mAh cm^(-2).Furthermore,the full cell with activated carbon cathodes exhibited a high specific capacity of 80.5 mAh g^(-1)and outstanding cycling stability without capacity decay after 15000 cycles at a high current density of 5 A g^(-1).The superior electrochemical performance exceeded that of most reported papers.Consequently,our synthesized zincophilic interlayer with the unique structure has superior prospects for application in stabilizing zinc anodes and prolonging the lifespan of batteries.
基金Natural Science Foundation of Hunan Province (No.2020JJ4734)High Performance Computing Center of Central South University。
文摘The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.
基金the partial financial support from the National Natural Science Foundation of China(21935003 and 21805182)National Key Research and Development Plan(2016YFB0901503)+1 种基金Shanghai Pujiang Program(18PJ1403800)the support from the Hundreds of Talents program of Sun Yat-sen University。
文摘Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.
基金This work was financially supported by Hong Kong Innovation&Technology Fund(ITS/031/18)National Key R&D Program of China(2016YFB0700600)+1 种基金Soft Science Research Project of Guangdong Province(2017B030301013)Shenzhen Science and Technology Research Grant(ZDSYS201707281026184).
文摘Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes that originates from dendrite growth,surface passivation and corrosion,severely hinders the further development of ZBs.To tackle these issues,here we report a Janus separator based on a Zn-ion conductive metal-organic framework(MOF)and reduced graphene oxide(rGO),which is able to regulate uniform Zn2+flux and electron conduction simultaneously during battery operation.Facilitated by the MOF/rGO bifunctional interlayers,the Zn anodes demonstrate stable plating/stripping behavior(over 500 h at 1 mA cm^(−2)),high Coulombic efficiency(99.2%at 2 mA cm^(−2) after 100 cycles)and reduced redox barrier.Moreover,it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface.Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells,which deliver nearly 100%capacity retention after 2000 cycles at 4 A g^(−1) and high power density over 10 kW kg^(−1).This work provides a feasible route to the high-performance Zn anodes for ZBs.
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.
