Zinc-ion batteries(ZIBs)is a promising electrical energy storage candidate due to its eco-friendliness,low cost,and intrinsic safety,but on the cathode the element dissolution and the formation of irreversible product...Zinc-ion batteries(ZIBs)is a promising electrical energy storage candidate due to its eco-friendliness,low cost,and intrinsic safety,but on the cathode the element dissolution and the formation of irreversible products,and on the anode the growth of dendrite as well as irreversible products hinder its practical application.Herein,we propose a new type of the inorganic highly concentrated colloidal electrolytes(HCCE)for ZIBs promoting simultaneous robust protection of both cathode/anode leading to an effective suppression of element dissolution,dendrite,and irreversible products growth.The new HCCE has high Zn^(2+)ion transference number(0.64)endowed by the limitation of SO4^(2−),the competitive ion conductivity(1.1×10^(–2) S cm^(−1))and Zn2+ion diffusion enabled by the uniform pore distribution(3.6 nm)and the limited free water.The Zn/HCCE/α-MnO2 cells exhibit high durability under both high and low current densities,which is almost 100%capacity retention at 200 mA g^(−1) after 400 cycles(290 mAh g^(−1))and 89%capacity retention under 500 mA g^(−1) after 1000 cycles(212 mAh g^(−1)).Considering material sustainability and batteries’high performances,the colloidal electrolyte may provide a feasible substitute beyond the liquid and all-solid-state electrolyte of ZIBs.展开更多
Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation ...Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation kinetics of Zn2+pose challenges for further development.Herein,highly reversible aqueous ZIBs are constructed with layered hydrated vanadium oxide as a cathode material.The electrochemical performances are further tested with the optimized electrolyte of 3M Zn(CF3SO3)2 and a cut-off voltage of 0.4 to 1.3 V,exhibiting a remarkable capacity of 290mAh g−1 at 0.5Ag−1,and long-term cycling stability at high current density.Furthermore,the Zn2+storage mechanism of V3O7⋅H2O is recognized as a highly reversible(de)intercalation process with good structural stability,implying the potential application in the field of large-scale energy storage.展开更多
Benefiting from the advantageous features of high safety,abundant reserves,low cost,and high energy density,aqueous Zn-based rechargeable batteries(AZBs)have received extensive attention as promising candidates for en...Benefiting from the advantageous features of high safety,abundant reserves,low cost,and high energy density,aqueous Zn-based rechargeable batteries(AZBs)have received extensive attention as promising candidates for energy storage.To achieve high-performance AZBs with high reversibility and energy density,great efforts have been devoted to overcoming their drawbacks by focusing on the modification of electrode materials and electrolytes.Based on different cathode materials and aqueous electrolytes,the development of aqueous AZBs with different redox mechanisms are discussed in this review,including insertion/extraction chemistries(e.g.,Zn^(2+),alkali metal ion,H^(+),NH_(4)^(+),and so forth dissolution/deposition reactions(e.g.,MnO_(2)/Mn^(2+)),redox couples in flow batteries(e.g.,I_(3)/3I,Br_(2)/Br,and so forth),oxygen electrochemistry(e.g.,O_(2)/OH,O_(2)/O_(2)2),and carbon dioxide electrochemistry(e.g.,CO_(2)/CO,CO_(2)/HCOOH).In particular,the basic reaction mechanisms,issues with the Zn electrode,aqueous electrolytes,and cathode materials as well as their design strategies are systematically reviewed.Finally,the remaining challenges faced by AZBs are summarized,and perspectives for further investigations are proposed.展开更多
Aqueous zinc-ion batteries(AZIBs)can be one of the most promising electrochemical energy storage devices for being non-flammable,low-cost,and sustainable.However,the challenges of AZIBs,including dendrite growth,hydro...Aqueous zinc-ion batteries(AZIBs)can be one of the most promising electrochemical energy storage devices for being non-flammable,low-cost,and sustainable.However,the challenges of AZIBs,including dendrite growth,hydrogen evolution,corrosion,and passivation of zinc anode during charging and discharging processes,must be overcome to achieve high cycling performance and stability in practical applications.In this work,we utilize a dual-func-tional organic additive cyclohexanedodecol(CHD)to firstly establish[Zn(H2O)5(CHD)]2+complex ion in an aqueous Zn electrolyte and secondly build a robust protection layer on the Zn surface to overcome these dilemmas.Systematic experiments and theoretical calculations are carried out to interpret the working mechanism of CHD.At a very low concentration of 0.1 mg mL^(−1) CHD,long-term reversible Zn plating/stripping could be achieved up to 2200 h at 2 mA cm^(−2),1000 h at 5 mA cm^(−2),and 650 h at 10 mA cm^(−2) at the fixed capacity of 1 mAh cm^(−2).When matched with V_(2)O_(5) cathode,the resultant AZIBs full cell with the CHD-modified electrolyte presents a high capacity of 175 mAh g^(−1) with the capacity retention of 92%after 2000 cycles under 2 A g^(−1).Such a performance could enable the commercialization of AZIBs for applications in grid energy storage and industrial energy storage.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
Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechan...Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.展开更多
In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development o...In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development of electrochromic-energy storage systems designed to visualize electrochemical charging and discharging processes.The conventional electrochromic-energy storage devices primarily integrated supercapacitors,known for their high power density,to enable rapid color contrast.However,the low energy density of supercapacitors restricts overall energy storage capacity,acting as a significant barrier to expanding the application range of such systems.In this review,we introduce electrochromic zinc(Zn)-ion battery systems,which effectively overcome the limitation of low energy density,and provide illustrative examples of their applicability across diverse fields.Although many recent research works are present for electrochromic Zn-ion batteries,little review has so far taken place.Our objective is to discuss on the current progress and future directions for electrochromic Zn-ion batteries,which are applicable for wearable electronics applications and energy storage systems.This review provides an initial milestone for future researchers in electrochromic energy storage and zinc-ion batteries,which will lead to a stream of future works related to them.展开更多
Cu-based chalcogenide materials exhibit significant promise for the development of Zn-metal-free anode materials for aqueous Zn-ion batteries (AZIBs). Here, we present the establishment of an efficient and universal s...Cu-based chalcogenide materials exhibit significant promise for the development of Zn-metal-free anode materials for aqueous Zn-ion batteries (AZIBs). Here, we present the establishment of an efficient and universal strategy that capitalizes on the pyrolysis of copper nanoclusters to fabricate conversion-type Cu_(7)S_(4) anodes engineered for AZIBs, showcasing outstanding electrochemical performance. Furthermore, by exploiting ligand engineering, we enable the precise control of both the type of molecular fragments generated during nanocluster pyrolysis, thus enabling the manipulation of vacancy concentrations and ion/electron migration in the resultant pyrolysis products. In contrast to the direct pyrolysis of metal salts and ligands, the products derived from copper nanoclusters exhibit enhanced specific capacity, rate performance, and overall stability. This research offers valuable insights for the development of novel electrode materials through the pyrolysis of atomically precise nanoclusters.展开更多
In recent years,rechargeable zinc-ion batteries(ZIBs)are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost.Nevertheless,the in-depth de...In recent years,rechargeable zinc-ion batteries(ZIBs)are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost.Nevertheless,the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues,such as the dissolution and structure collapse of cathode materials,the formation of by-products,severe anode corrosion,passivation,and the growth of zinc dendrites.The covalent organic frameworks(COFs)can solve the above problems to a certain extent owing to their ideal characteristics,such as rigid structure,insolubility,high porosity,and abundant active sites.COFs,as advanced materials for ZIBs,have attracted researchers'attention.In this review,we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs,which would provide a reference for the in-depth research of COFs.In addition,we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs.Finally,we discussed the challenges and solutions in the development of COF materials,which would provide constructive insights into the future direction of COFs.展开更多
Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost ...Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost for manufacturing fbered cathode.In this work,we demonstrated gamma manganese oxide(ɣ-MnO_(2))/reduced graphene oxide(rGO)fbered cathode fabrication using facile and cost-efective fber production and active material coating techniques.Specifcally,rGO fbers were fabricated via wet spinning,followed by chemical reduction with hydroiodic acid(HI).The synthesized rGO fber bundle was then dip-coated with a mixture ofɣ-MnO_(2),carbon black or multi-walled carbon nanotubes,and xanthan gum or polyvinylidene fuoride binder to obtainɣ-MnO_(2)/rGO fbered cathode.We studied the efect of binders and conductive materials on physical properties and electrochemical performance of the fbered cathode.It was found that hydrophobic binder had more benefts than hydrophilic binder by providing higher active material loading,better coating layer homogeneity,and more stable electrochemical performance.Cable-shaped Zn-ion batteries(CSZIBs)were then assembled by using theɣ-MnO_(2)/rGO fbered cathode,Zn wire anode,and xanthan gum polymeric gel electrolyte with 2 M ZnSO_(4) and 0.2 M MnSO_(4) salts without a separator.We investigated the battery assembling procedure on a glass slide(prototype ZIB)and in a plastic tube(cable-shaped ZIB),and evaluated their electrochemical performance.The CSZIB showed promising maximum capacity of~230 mAh/g with moderate cycling stability(80%capacity retention after 200 cycles)and high fexibility by maintaining the potential after consecutive pressing for 200 times under controlled pressing distance,duration,and testing speed.Finally,we explored ion intercalation behaviours and proposed a H^(+)/Zn^(2+)co-intercalation mechanism in ZIB withɣ-MnO_(2) active material.展开更多
水系锌离子电池(ZIBs)以其低成本、高安全性和环境友好的优点受到了研究者的广泛关注,成为大规模电化学储能系统的理想选择之一。然而锌金属负极在应用时面临着锌枝晶生长、腐蚀反应和副反应等难以克服的障碍,严重制约了水系锌离子电池...水系锌离子电池(ZIBs)以其低成本、高安全性和环境友好的优点受到了研究者的广泛关注,成为大规模电化学储能系统的理想选择之一。然而锌金属负极在应用时面临着锌枝晶生长、腐蚀反应和副反应等难以克服的障碍,严重制约了水系锌离子电池的发展。探索可替代锌金属的储锌负极是应对上述问题的有效策略,因此研究者围绕过渡金属氧化物、硫化物和导电聚合物开展了深入研究。以TiX_(2)(X=S,Se)为代表的二维过渡金属硫族化合物(TMDs)具有较大的层间距和快速的离子传输通道,可作为锌离子电池的负极,但其储锌反应机制尚未得到完整的揭示。在本文中,我们使用密度泛函理论(DFT)计算方法系统地研究锌离子在TiX_(2)中的嵌入反应。首先我们采用群论去描述嵌锌TiX_(2)的稳定层间构型的特点,定义了一个依赖于超胞并且只涉及平移旋转两种对称操作的群,其子群可以用来描述层间构型的对称性,而且用来描述最稳定构型的子群总是倾向于有最大的阶数。基于该计算得到的一系列对应于不同放电深度的TiX_(2)的稳定结构,我们发现TiS_(2)和TiSe_(2)两种材料在锌嵌入/脱出过程中的开路电压(OCV)均低于0.5V。态密度(DOS)的计算结果表明TiX_(2)具有很好的电子导电性,而分波态密度(PDOS)的结果显示随着锌的嵌入闭壳层的Ti^(4+)还原成开壳层的Ti^(3+),并且伴随着Zn―X键的生成。Bader电荷分析的结果表明随着X的嵌入,X相比Ti得到了更多的负电荷,意味着X也参与了TiX_(2)的氧化还原过程。爬坡弹性带方法(CINEB)计算的结果证实了Zn^(2+)在TiX_(2)中具有较低的扩散能垒(对于TiS_(2)是0.333 e V,对于TiSe_(2)是0.338e V)。本文的研究结果不仅从本质上证明了TiX_(2)适合作为锌离子电池的嵌锌负极材料,而且为其他高性能TMDs电池材料的DFT研究提供了新的见解。展开更多
Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs ...Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs is still plagued by the low specific capacity and poor rate capability.Herein,highly crystalline Mn2O3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs.The coordination degree between Mn2+and citric acid ligand plays a crucial role in the formation of the mesostructure,and the pore sizes can be easily tuned from 3.2 to 7.3 nm.Ascribed to the unique feature of nanoporous architectures,excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes.The Mn2O3 electrode exhibits high reversible capacity(233 mAh g−1 at 0.3 A g−1),superior rate capability(162 mAh g−1 retains at 3.08 A g−1)and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g−1.Moreover,the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods.These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.展开更多
Among many aqueous batteries,flexible zinc-ion(Zn-ion)battery becomes the focus owing to the merits of low cost,non-toxicity,and safety.Here,a Zn dendrite-suppressible hydrogel electrolyte with both flexible and self-...Among many aqueous batteries,flexible zinc-ion(Zn-ion)battery becomes the focus owing to the merits of low cost,non-toxicity,and safety.Here,a Zn dendrite-suppressible hydrogel electrolyte with both flexible and self-healing properties is developed via photoinitiated polymerization.The cross-linked structure of the polyacrylamide-N,N'-methylenebisacrylamide(PAM-MBA)-Zn/Mn hydrogel endows an enlarged chemical stable window,high ionic conductivity,and low polarization potential.After cycling at the current density of 0.5 mA·cm^(−2)for 250 h,Zn‖Zn symmetrical cell based on PAM-MBA-Zn/Mn electrolyte delivers a low polarization of 40 mV.The suppressed dendrite growth is ascribed to the uniform Zn deposition/stripping on anode.The galvanostatic intermittent titration technique curves display that the Zn-ion battery constructed by the PAM-MBA-Zn/Mn hydrogel electrolyte,free-standing FeVO_(4)/carbon cloth cathode,and Zn nanosheets/carbon cloth anode presents low reaction resistance and fast diffusion coefficient,indicating good endurance of cycling at high current densities.The battery with PAM-MBA-Zn/Mn hydrogel electrolyte presents a good flexible and self-healing performance.After bending 0°,60°,90°,and 180°for 30 times,batteries deliver stable capacities.Even cutting into ten pieces,the battery could self-heal and display a potential retention of 93.7%compared to the fresh cell.A good rate-performance is also achieved.After cutting/healing three times during cycling,capacity recovers well compared to the first-time cutting/healing.Moreover,the battery exhibits good flexibility using in an electric watch,indicating a promising potential for wearable electronics.展开更多
Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has no...Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has not been studied extensively and the underlying mechanism and theoretical basis of this type of batteries are not well understood.Herein,a highly active cobalt-doped Ni_(3)S_(2) porous nanocone framework(C12NS)is designed and demonstrated as a zinc-ion battery electrode.First-principles calculation and experiments reveal that the cobalt dopant improves the battery properties greatly.The assembled flexible zinc-ion battery exhibits a high specific capacity of 453.3 mAh g^(−1)at a current density of 0.4 A g^(−1)in as well as excellent cycling stability as manifested by a capacity retention ratio of 89.5%at a current density of 4 A g^(−1)after 5000 cycles.The peak energy density of 553.9 Wh kg^(−1)is also superior to those of most recently reported NiCo-based zinc-ion batteries.More importantly,the flexible battery can be operated under severe mechanical bending and even continues to work after physical puncturing without showing leakage.These exciting results not only reveal a novel design of cathode materials for zinc-based batteries,but also suggest their immense commercial potential in portable and wearable electronics.展开更多
Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory ...Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory cycling performance.The polyoxometalates perform formidable redox stability and able to participate in multi-electron transfer,which was well-suited for energy storage.Herein,a bicomponent polyoxometalate-derivative KNiVO(K_(2)[Ni(H_(2)O)_(6)]_(2)[V_(10)O_(28)]·_(4)H_(2)O polyoxometalates after annealing)is firstly demonstrated as a cathode material for aqueous ZIBs.The layered KV_(3)O_(8)(KVO)In the bi-component material constitutes Zn^(2+) migration and storage channels(K^(+) were substantially replaced by Zn^(2+) in the activation phase),and the three-dimensional NiV_(3)O_(8)(NiVO)part acts as skeleton to stabilize the ion channels,which assist the cell to demonstrate a high-rate capacity and specific energy of229.4 mAh/g and satisfactory cyclability(capacity retention of 99.1%after 4500 cycles at a current density of 4 A/g).These results prove the feasibility of POM as cathode materials precursor and put forward a novel pattern of the Zn^(2+)storage mechanism in the activated-KNiVO clusters,which also provide a new route for selecting or designing high-performance cathode for aqueous ZIBs and other advanced battery systems.展开更多
锰基氧化物作为锌离子电池正极具有高比容量和低成本等优点,但在电化学循环过程中不可逆相变、锰的溶解和电极/电解质界面不稳定导致其在小电流密度、深度放电条件下的循环性能差.针对以上问题,合成了三维(3D)多孔MnOx立方盒子,并在其...锰基氧化物作为锌离子电池正极具有高比容量和低成本等优点,但在电化学循环过程中不可逆相变、锰的溶解和电极/电解质界面不稳定导致其在小电流密度、深度放电条件下的循环性能差.针对以上问题,合成了三维(3D)多孔MnOx立方盒子,并在其表面包覆In_(2)O_(3)层,获得3D多孔MnO_(x)@In_(2)O_(3)立方盒子.结果显示,MnO_(x)@In_(2)O_(3)立方盒子具有大量孔径约10 nm左右的孔,有利于H^(+)和Zn^(2+)的快速传输;In2O3包覆层均匀包覆于3D多孔MnO_(x)立方盒子的孔壁上,有利于抑制MnO_(x)在电化学循环过程中的不可逆相变和锰的溶解,稳定电极/电解质界面.电化学测试结果表明,该3D多孔MnO_(x)@In_(2)O_(3)电极在0.3 A/g的小电流密度、深度放电条件下能稳定循环400次以上,容量保持260 m A·h/g;在1.8 A/g电流密度下可稳定循环4000次以上,容量保持81m A·h/g;即使在高电流密度6.0 A/g下仍保持73.4 m A·h/g的高可逆容量.恒电流间隙滴定(GITT)和循环伏安测试结果表明,3D多孔MnO_(x)@In_(2)O_(3)电极比3D多孔MnO_(x)具有更高的离子扩散速率,有利于提升其高倍率容量.电化学阻抗谱结果表明,3D多孔MnO_(x)@In_(2)O_(3)电极具有比3D多孔MnO_(x)更稳定的电极/电解质界面,有利于提升其循环寿命.2000次循环后的扫描电子显微镜(SEM)结果表明,MnO_(x)@In_(2)O_(3)电极表面仍分布少量In_(2)O_(3),以确保电极/电解质界面和循环的稳定性.展开更多
基金National Natural Science Foundation of China(Grant Nos.51972346,51932011,51922038,and 51672078)Hunan Outstanding Youth Talents(No.2019JJ20005)+1 种基金the Program of Youth Talent Support for Hunan Province(2020RC3011)Innovation-Driven Project of Central South University(No.2020CX024).
文摘Zinc-ion batteries(ZIBs)is a promising electrical energy storage candidate due to its eco-friendliness,low cost,and intrinsic safety,but on the cathode the element dissolution and the formation of irreversible products,and on the anode the growth of dendrite as well as irreversible products hinder its practical application.Herein,we propose a new type of the inorganic highly concentrated colloidal electrolytes(HCCE)for ZIBs promoting simultaneous robust protection of both cathode/anode leading to an effective suppression of element dissolution,dendrite,and irreversible products growth.The new HCCE has high Zn^(2+)ion transference number(0.64)endowed by the limitation of SO4^(2−),the competitive ion conductivity(1.1×10^(–2) S cm^(−1))and Zn2+ion diffusion enabled by the uniform pore distribution(3.6 nm)and the limited free water.The Zn/HCCE/α-MnO2 cells exhibit high durability under both high and low current densities,which is almost 100%capacity retention at 200 mA g^(−1) after 400 cycles(290 mAh g^(−1))and 89%capacity retention under 500 mA g^(−1) after 1000 cycles(212 mAh g^(−1)).Considering material sustainability and batteries’high performances,the colloidal electrolyte may provide a feasible substitute beyond the liquid and all-solid-state electrolyte of ZIBs.
基金This study was supported by the National Natural Science Foundation of China(Grant no.51932011,51972346,51802356,and 51872334)Innovation-Driven Project of Central South University(No.2020CX024).
文摘Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation kinetics of Zn2+pose challenges for further development.Herein,highly reversible aqueous ZIBs are constructed with layered hydrated vanadium oxide as a cathode material.The electrochemical performances are further tested with the optimized electrolyte of 3M Zn(CF3SO3)2 and a cut-off voltage of 0.4 to 1.3 V,exhibiting a remarkable capacity of 290mAh g−1 at 0.5Ag−1,and long-term cycling stability at high current density.Furthermore,the Zn2+storage mechanism of V3O7⋅H2O is recognized as a highly reversible(de)intercalation process with good structural stability,implying the potential application in the field of large-scale energy storage.
基金Centre Québéco is sur les Materiaux FonctionnelsChina Scholarship Council+5 种基金Fonds de Recherche du Québec-Nature et TechnologiesNatural Sciences and Engineering Research Council of CanadaClermont Auvergne MétropoleUniversitéClermont AuvergneI-Site CAP2025Institut National de la Recherche Scientifique。
文摘Benefiting from the advantageous features of high safety,abundant reserves,low cost,and high energy density,aqueous Zn-based rechargeable batteries(AZBs)have received extensive attention as promising candidates for energy storage.To achieve high-performance AZBs with high reversibility and energy density,great efforts have been devoted to overcoming their drawbacks by focusing on the modification of electrode materials and electrolytes.Based on different cathode materials and aqueous electrolytes,the development of aqueous AZBs with different redox mechanisms are discussed in this review,including insertion/extraction chemistries(e.g.,Zn^(2+),alkali metal ion,H^(+),NH_(4)^(+),and so forth dissolution/deposition reactions(e.g.,MnO_(2)/Mn^(2+)),redox couples in flow batteries(e.g.,I_(3)/3I,Br_(2)/Br,and so forth),oxygen electrochemistry(e.g.,O_(2)/OH,O_(2)/O_(2)2),and carbon dioxide electrochemistry(e.g.,CO_(2)/CO,CO_(2)/HCOOH).In particular,the basic reaction mechanisms,issues with the Zn electrode,aqueous electrolytes,and cathode materials as well as their design strategies are systematically reviewed.Finally,the remaining challenges faced by AZBs are summarized,and perspectives for further investigations are proposed.
基金financial support from the Australia Research Council Discovery Projects(DP210103266)of Australiasupported by computational resources provided by the Australian Government through the National Computational Infrastructure(NCI)under the National Computational Merit Allocation Scheme and the Pawsey Supercomputing Centre with funding from the Australian Government and the Government of Western Australia。
文摘Aqueous zinc-ion batteries(AZIBs)can be one of the most promising electrochemical energy storage devices for being non-flammable,low-cost,and sustainable.However,the challenges of AZIBs,including dendrite growth,hydrogen evolution,corrosion,and passivation of zinc anode during charging and discharging processes,must be overcome to achieve high cycling performance and stability in practical applications.In this work,we utilize a dual-func-tional organic additive cyclohexanedodecol(CHD)to firstly establish[Zn(H2O)5(CHD)]2+complex ion in an aqueous Zn electrolyte and secondly build a robust protection layer on the Zn surface to overcome these dilemmas.Systematic experiments and theoretical calculations are carried out to interpret the working mechanism of CHD.At a very low concentration of 0.1 mg mL^(−1) CHD,long-term reversible Zn plating/stripping could be achieved up to 2200 h at 2 mA cm^(−2),1000 h at 5 mA cm^(−2),and 650 h at 10 mA cm^(−2) at the fixed capacity of 1 mAh cm^(−2).When matched with V_(2)O_(5) cathode,the resultant AZIBs full cell with the CHD-modified electrolyte presents a high capacity of 175 mAh g^(−1) with the capacity retention of 92%after 2000 cycles under 2 A g^(−1).Such a performance could enable the commercialization of AZIBs for applications in grid energy storage and industrial energy storage.
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This work was financially supported by the National Natural Science Foundation of China(22075171)Natural Science Foundation of Shanghai(23ZR1423400)The firstprinciples calculations were supported by the High Performance Computing Center of Shanghai University.
文摘Hydrogen evolution reaction(HER)has become a key factor affecting the cycling stability of aqueous Zn-ion batteries,while the corresponding fundamental issues involving HER are still unclear.Herein,the reaction mechanisms of HER on various crystalline surfaces have been investigated by first-principle calculations based on density functional theory.It is found that the Volmer step is the ratelimiting step of HER on the Zn(002)and(100)surfaces,while,the reaction rates of HER on the Zn(101),(102)and(103)surfaces are determined by the Tafel step.Moreover,the correlation between HER activity and the generalized coordination number(CN)of Zn at the surfaces has been revealed.The relatively weaker HER activity on Zn(002)surface can be attributed to the higher CN of surface Zn atom.The atomically uneven Zn(002)surface shows significantly higher HER activity than the flat Zn(002)surface as the CN of the surface Zn atom is lowered.The CN of surface Zn atom is proposed as a key descriptor of HER activity.Tuning the CN of surface Zn atom would be a vital strategy to inhibit HER on the Zn anode surface based on the presented theoretical studies.Furthermore,this work provides a theoretical basis for the in-depth understanding of HER on the Zn surface.
基金supported by funding from Bavarian Center for Battery Technology(Bay Batt),Bayerisch-Tschechische Hochschulagentur(BTHA)(BTHA-AP-2022-45,BTHA-AP-2023-5,BTHA-AP2023-12,and BTHA-AP-2023-38)the University of BayreuthDeakin University Joint Ph.D.Program,Bayerische Forschungallianz(Bay FOR)(Bay Int An_UBT_2023_84)+2 种基金BK21 program from National Research Foundation of Korea,Erasmus+program from the European Union,Ministry of Education,Science and Technology as part of the Higher Education for Economic Transformation(HEET)Project(World Bank)Verband der Chemischen Industrie(Fonds der Chemischen Industrie,No.661740)collaboration project funding from Kangwon National University and LINC 3.0 Research Center,and the Deutsche Forschungsgemeinschaft(DFG,project number:533115776)。
文摘In recent times,future energy storage systems demand a multitude of functionalities beyond their traditional energy storage capabilities.In line with this technological shift,there is active research and development of electrochromic-energy storage systems designed to visualize electrochemical charging and discharging processes.The conventional electrochromic-energy storage devices primarily integrated supercapacitors,known for their high power density,to enable rapid color contrast.However,the low energy density of supercapacitors restricts overall energy storage capacity,acting as a significant barrier to expanding the application range of such systems.In this review,we introduce electrochromic zinc(Zn)-ion battery systems,which effectively overcome the limitation of low energy density,and provide illustrative examples of their applicability across diverse fields.Although many recent research works are present for electrochromic Zn-ion batteries,little review has so far taken place.Our objective is to discuss on the current progress and future directions for electrochromic Zn-ion batteries,which are applicable for wearable electronics applications and energy storage systems.This review provides an initial milestone for future researchers in electrochromic energy storage and zinc-ion batteries,which will lead to a stream of future works related to them.
基金supported by the National Natural Science Foundation of China(Nos.21825106,22209154,and 22001236)Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(No.234000510007)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(No.19IRTSTHN022)。
文摘Cu-based chalcogenide materials exhibit significant promise for the development of Zn-metal-free anode materials for aqueous Zn-ion batteries (AZIBs). Here, we present the establishment of an efficient and universal strategy that capitalizes on the pyrolysis of copper nanoclusters to fabricate conversion-type Cu_(7)S_(4) anodes engineered for AZIBs, showcasing outstanding electrochemical performance. Furthermore, by exploiting ligand engineering, we enable the precise control of both the type of molecular fragments generated during nanocluster pyrolysis, thus enabling the manipulation of vacancy concentrations and ion/electron migration in the resultant pyrolysis products. In contrast to the direct pyrolysis of metal salts and ligands, the products derived from copper nanoclusters exhibit enhanced specific capacity, rate performance, and overall stability. This research offers valuable insights for the development of novel electrode materials through the pyrolysis of atomically precise nanoclusters.
基金financially supported by the National Natural Science Foundation of China(No.61904073)Spring City Plan-Special Program for Young Talents(No.ZX20210014)+3 种基金Yunnan Talents Support Plan for Yong TalentsYunnan Local Colleges Applied Basic Research Projects(No.202101BA070001–138)Frontier Research Team of Kunming University 2023Key Laboratory of Artificial Microstructures in Yunnan Higher Education。
文摘In recent years,rechargeable zinc-ion batteries(ZIBs)are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost.Nevertheless,the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues,such as the dissolution and structure collapse of cathode materials,the formation of by-products,severe anode corrosion,passivation,and the growth of zinc dendrites.The covalent organic frameworks(COFs)can solve the above problems to a certain extent owing to their ideal characteristics,such as rigid structure,insolubility,high porosity,and abundant active sites.COFs,as advanced materials for ZIBs,have attracted researchers'attention.In this review,we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs,which would provide a reference for the in-depth research of COFs.In addition,we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs.Finally,we discussed the challenges and solutions in the development of COF materials,which would provide constructive insights into the future direction of COFs.
基金This work was fnancially supported by Wilson College of Textiles,North Carolina State University,National Nanotechnology Center(NANOTEC),and National Energy Technology Center(ENTEC).
文摘Cable/fber-shaped Zn-ion batteries are designed to power wearable electronics that require high fexibility to operate on human body.However,one of technical challenges of these devices is the complexity and high cost for manufacturing fbered cathode.In this work,we demonstrated gamma manganese oxide(ɣ-MnO_(2))/reduced graphene oxide(rGO)fbered cathode fabrication using facile and cost-efective fber production and active material coating techniques.Specifcally,rGO fbers were fabricated via wet spinning,followed by chemical reduction with hydroiodic acid(HI).The synthesized rGO fber bundle was then dip-coated with a mixture ofɣ-MnO_(2),carbon black or multi-walled carbon nanotubes,and xanthan gum or polyvinylidene fuoride binder to obtainɣ-MnO_(2)/rGO fbered cathode.We studied the efect of binders and conductive materials on physical properties and electrochemical performance of the fbered cathode.It was found that hydrophobic binder had more benefts than hydrophilic binder by providing higher active material loading,better coating layer homogeneity,and more stable electrochemical performance.Cable-shaped Zn-ion batteries(CSZIBs)were then assembled by using theɣ-MnO_(2)/rGO fbered cathode,Zn wire anode,and xanthan gum polymeric gel electrolyte with 2 M ZnSO_(4) and 0.2 M MnSO_(4) salts without a separator.We investigated the battery assembling procedure on a glass slide(prototype ZIB)and in a plastic tube(cable-shaped ZIB),and evaluated their electrochemical performance.The CSZIB showed promising maximum capacity of~230 mAh/g with moderate cycling stability(80%capacity retention after 200 cycles)and high fexibility by maintaining the potential after consecutive pressing for 200 times under controlled pressing distance,duration,and testing speed.Finally,we explored ion intercalation behaviours and proposed a H^(+)/Zn^(2+)co-intercalation mechanism in ZIB withɣ-MnO_(2) active material.
文摘水系锌离子电池(ZIBs)以其低成本、高安全性和环境友好的优点受到了研究者的广泛关注,成为大规模电化学储能系统的理想选择之一。然而锌金属负极在应用时面临着锌枝晶生长、腐蚀反应和副反应等难以克服的障碍,严重制约了水系锌离子电池的发展。探索可替代锌金属的储锌负极是应对上述问题的有效策略,因此研究者围绕过渡金属氧化物、硫化物和导电聚合物开展了深入研究。以TiX_(2)(X=S,Se)为代表的二维过渡金属硫族化合物(TMDs)具有较大的层间距和快速的离子传输通道,可作为锌离子电池的负极,但其储锌反应机制尚未得到完整的揭示。在本文中,我们使用密度泛函理论(DFT)计算方法系统地研究锌离子在TiX_(2)中的嵌入反应。首先我们采用群论去描述嵌锌TiX_(2)的稳定层间构型的特点,定义了一个依赖于超胞并且只涉及平移旋转两种对称操作的群,其子群可以用来描述层间构型的对称性,而且用来描述最稳定构型的子群总是倾向于有最大的阶数。基于该计算得到的一系列对应于不同放电深度的TiX_(2)的稳定结构,我们发现TiS_(2)和TiSe_(2)两种材料在锌嵌入/脱出过程中的开路电压(OCV)均低于0.5V。态密度(DOS)的计算结果表明TiX_(2)具有很好的电子导电性,而分波态密度(PDOS)的结果显示随着锌的嵌入闭壳层的Ti^(4+)还原成开壳层的Ti^(3+),并且伴随着Zn―X键的生成。Bader电荷分析的结果表明随着X的嵌入,X相比Ti得到了更多的负电荷,意味着X也参与了TiX_(2)的氧化还原过程。爬坡弹性带方法(CINEB)计算的结果证实了Zn^(2+)在TiX_(2)中具有较低的扩散能垒(对于TiS_(2)是0.333 e V,对于TiSe_(2)是0.338e V)。本文的研究结果不仅从本质上证明了TiX_(2)适合作为锌离子电池的嵌锌负极材料,而且为其他高性能TMDs电池材料的DFT研究提供了新的见解。
基金the Young Thousand Talented Program and the National Natural Science Foundation of China (21671073 and 21621001)the “111” Project of the Ministry of Education of China (B17020)Program for JLU Science and Technology Innovative Research Team
文摘Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs is still plagued by the low specific capacity and poor rate capability.Herein,highly crystalline Mn2O3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs.The coordination degree between Mn2+and citric acid ligand plays a crucial role in the formation of the mesostructure,and the pore sizes can be easily tuned from 3.2 to 7.3 nm.Ascribed to the unique feature of nanoporous architectures,excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes.The Mn2O3 electrode exhibits high reversible capacity(233 mAh g−1 at 0.3 A g−1),superior rate capability(162 mAh g−1 retains at 3.08 A g−1)and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g−1.Moreover,the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods.These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.
基金supported by the National Key Research and Development Program of China(No.2017YFA0402904)Key Research and Development Program of Wuhu(No.2022YF53)+1 种基金Natural Science Research Project for Universities in Anhui Province(No.2022AH050176)Anhui Provincial Quality Engineering for Cooperative Practice Education Base(No.2022xqhz020).
文摘Among many aqueous batteries,flexible zinc-ion(Zn-ion)battery becomes the focus owing to the merits of low cost,non-toxicity,and safety.Here,a Zn dendrite-suppressible hydrogel electrolyte with both flexible and self-healing properties is developed via photoinitiated polymerization.The cross-linked structure of the polyacrylamide-N,N'-methylenebisacrylamide(PAM-MBA)-Zn/Mn hydrogel endows an enlarged chemical stable window,high ionic conductivity,and low polarization potential.After cycling at the current density of 0.5 mA·cm^(−2)for 250 h,Zn‖Zn symmetrical cell based on PAM-MBA-Zn/Mn electrolyte delivers a low polarization of 40 mV.The suppressed dendrite growth is ascribed to the uniform Zn deposition/stripping on anode.The galvanostatic intermittent titration technique curves display that the Zn-ion battery constructed by the PAM-MBA-Zn/Mn hydrogel electrolyte,free-standing FeVO_(4)/carbon cloth cathode,and Zn nanosheets/carbon cloth anode presents low reaction resistance and fast diffusion coefficient,indicating good endurance of cycling at high current densities.The battery with PAM-MBA-Zn/Mn hydrogel electrolyte presents a good flexible and self-healing performance.After bending 0°,60°,90°,and 180°for 30 times,batteries deliver stable capacities.Even cutting into ten pieces,the battery could self-heal and display a potential retention of 93.7%compared to the fresh cell.A good rate-performance is also achieved.After cutting/healing three times during cycling,capacity recovers well compared to the first-time cutting/healing.Moreover,the battery exhibits good flexibility using in an electric watch,indicating a promising potential for wearable electronics.
基金jointly supported by the National Natural Science Foundation of China(Grant Nos.61176108 and 61774060)the Science and Technology Commission of Shanghai Municipality(Grant No.18DZ2270800)+1 种基金the City University of Hong Kong Strategic Research Grant(SRG)(Grant No.7005505)the support of the Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry(Grant No.[2015]-1098)。
文摘Flexible quasi-solid zinc-ion batteries(ZIBs)have large potential in power applications due to the low price,wearable nature,safety,and high capacity.However,the use of transition metal sulfide cathodes in ZIBs has not been studied extensively and the underlying mechanism and theoretical basis of this type of batteries are not well understood.Herein,a highly active cobalt-doped Ni_(3)S_(2) porous nanocone framework(C12NS)is designed and demonstrated as a zinc-ion battery electrode.First-principles calculation and experiments reveal that the cobalt dopant improves the battery properties greatly.The assembled flexible zinc-ion battery exhibits a high specific capacity of 453.3 mAh g^(−1)at a current density of 0.4 A g^(−1)in as well as excellent cycling stability as manifested by a capacity retention ratio of 89.5%at a current density of 4 A g^(−1)after 5000 cycles.The peak energy density of 553.9 Wh kg^(−1)is also superior to those of most recently reported NiCo-based zinc-ion batteries.More importantly,the flexible battery can be operated under severe mechanical bending and even continues to work after physical puncturing without showing leakage.These exciting results not only reveal a novel design of cathode materials for zinc-based batteries,but also suggest their immense commercial potential in portable and wearable electronics.
基金supported by the Natural Science Foundation of Hunan Province(No.2020JJ4684)the Fundamental Research Funds for the Central Universities of Central South University(No.2021zzts0522)the Recruitment Program of Global Youth Experts。
文摘Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory cycling performance.The polyoxometalates perform formidable redox stability and able to participate in multi-electron transfer,which was well-suited for energy storage.Herein,a bicomponent polyoxometalate-derivative KNiVO(K_(2)[Ni(H_(2)O)_(6)]_(2)[V_(10)O_(28)]·_(4)H_(2)O polyoxometalates after annealing)is firstly demonstrated as a cathode material for aqueous ZIBs.The layered KV_(3)O_(8)(KVO)In the bi-component material constitutes Zn^(2+) migration and storage channels(K^(+) were substantially replaced by Zn^(2+) in the activation phase),and the three-dimensional NiV_(3)O_(8)(NiVO)part acts as skeleton to stabilize the ion channels,which assist the cell to demonstrate a high-rate capacity and specific energy of229.4 mAh/g and satisfactory cyclability(capacity retention of 99.1%after 4500 cycles at a current density of 4 A/g).These results prove the feasibility of POM as cathode materials precursor and put forward a novel pattern of the Zn^(2+)storage mechanism in the activated-KNiVO clusters,which also provide a new route for selecting or designing high-performance cathode for aqueous ZIBs and other advanced battery systems.
文摘锰基氧化物作为锌离子电池正极具有高比容量和低成本等优点,但在电化学循环过程中不可逆相变、锰的溶解和电极/电解质界面不稳定导致其在小电流密度、深度放电条件下的循环性能差.针对以上问题,合成了三维(3D)多孔MnOx立方盒子,并在其表面包覆In_(2)O_(3)层,获得3D多孔MnO_(x)@In_(2)O_(3)立方盒子.结果显示,MnO_(x)@In_(2)O_(3)立方盒子具有大量孔径约10 nm左右的孔,有利于H^(+)和Zn^(2+)的快速传输;In2O3包覆层均匀包覆于3D多孔MnO_(x)立方盒子的孔壁上,有利于抑制MnO_(x)在电化学循环过程中的不可逆相变和锰的溶解,稳定电极/电解质界面.电化学测试结果表明,该3D多孔MnO_(x)@In_(2)O_(3)电极在0.3 A/g的小电流密度、深度放电条件下能稳定循环400次以上,容量保持260 m A·h/g;在1.8 A/g电流密度下可稳定循环4000次以上,容量保持81m A·h/g;即使在高电流密度6.0 A/g下仍保持73.4 m A·h/g的高可逆容量.恒电流间隙滴定(GITT)和循环伏安测试结果表明,3D多孔MnO_(x)@In_(2)O_(3)电极比3D多孔MnO_(x)具有更高的离子扩散速率,有利于提升其高倍率容量.电化学阻抗谱结果表明,3D多孔MnO_(x)@In_(2)O_(3)电极具有比3D多孔MnO_(x)更稳定的电极/电解质界面,有利于提升其循环寿命.2000次循环后的扫描电子显微镜(SEM)结果表明,MnO_(x)@In_(2)O_(3)电极表面仍分布少量In_(2)O_(3),以确保电极/电解质界面和循环的稳定性.
