Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during t...Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.展开更多
With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy stor...With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.展开更多
Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to dras...Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.展开更多
Zinc-ion batteries(ZIBs) are recognized as potential energy storage devices due to their advantages of low cost, high energy density, and environmental friendliness. However, zinc anodes are subject to unavoidable zin...Zinc-ion batteries(ZIBs) are recognized as potential energy storage devices due to their advantages of low cost, high energy density, and environmental friendliness. However, zinc anodes are subject to unavoidable zinc dendrites, passivation, corrosion, and hydrogen evolution reactions during the charging and discharging of batteries, becoming obstacles to the practical application of ZIBs. Appropriate zinc metal-free anodes provide a higher working potential than metallic zinc anodes, effectively solving the problems of zinc dendrites, hydrogen evolution, and side reactions during the operation of metallic zinc anodes. The improvement in the safety and cycle life of batteries creates conditions for further commercialization of ZIBs. Therefore, this work systematically introduces the research progress of zinc metal-free anodes in “rocking chair” ZIBs. Zinc metal-free anodes are mainly discussed in four categories: transition metal oxides,transition metal sulfides, MXene(two dimensional transition metal carbide) composites, and organic compounds, with discussions on their properties and zinc storage mechanisms. Finally, the outlook for the development of zinc metal-free anodes is proposed. This paper is expected to provide a reference for the further promotion of commercial rechargeable ZIBs.展开更多
Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framewo...Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.展开更多
Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high ...Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high electrochemical performance owing to the limited electronic conductivity,sluggish ion kinetics,and severe volume expansion during the insertion/extraction process of Zn^(2+).Herein,a series of V_(2)O_(3)nanospheres embedded N-doped carbon nanofiber structures with various V_(2)O_(3)spherical morphologies(solid,core-shell,hollow)have been designed for the first time by an electrospinning technique followed thermal treatments.The N-doped carbon nanofibers not only improve the electrical conductivity and the structural stability,but also provides encapsulating shells to prevent the vanadium dissolution and aggregation of V_(2)O_(3)particles.Furthermore,the varied morphological structures of V_(2)O_(3)with abundant oxygen vacancies can alleviate the volume change and increase the Zn^(2+)pathway.Besides,the phase transition between V_(2)O_(3)and Zn_XV_(2)O_(5-m)·n H_(2)O in the cycling was also certified.As a result,the as-obtained composite delivers excellent long-term cycle stability and enhanced rate performance for coin cells,which is also confirmed through density functional theory(DFT)calculations.Even assembled into flexible ZIBs,the sample still exhibits superior electrochemical performance,which may afford new design concept for flexible cathode materials of ZIBs.展开更多
Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely...Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.展开更多
Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for...Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.展开更多
The notorious growth of zinc dendrite and the water-induced corrosion of zinc metal anodes(ZMAs)restrict the practical development of aqueous zinc ion batteries(AZIBs).In this work,a zinc metallized,imide-pillared cov...The notorious growth of zinc dendrite and the water-induced corrosion of zinc metal anodes(ZMAs)restrict the practical development of aqueous zinc ion batteries(AZIBs).In this work,a zinc metallized,imide-pillared covalent organic framework(ZPC)protective film has been engineered as a stable Zn^(2+)ion-conducting interphase to modulate interfacial kinetics and suppress side reactions for ZMAs.Compared to bare Zn,ZPC@Zn exhibits a higher Zn^(2+)ionic conductivity,a larger Zn^(2+)transference number,a lower electronic conductivity,a smaller desolvation activation energy and correspondingly a significant suppression of corrosion,hydrogen evolution and Zn dendrites.Impressively,the ZPC@Zn||ZPC@Zn symmetric cell obtains a cycling lifespan over 3000 h under 5 mA cm^(-2)for 1 mA h cm^(-2).The ZPC@Zn||NH_(4)V_(4)O_(10)coin-type full battery delivers a specific capacity of 195.8 mA h g^(-1)with a retention rate of78.5%at 2 A g^(-1)after 1100 cycles,and the ZPC@Zn||NH_(4)V_(4)O_(10) pouch full cell shows a retention of70.1%in reversible capacity at 3 A g^(-1)after 1100 cycles.The present incorporation of imide-linked covalent organic frameworks in the surface modification of ZMAs will offer fresh perspectives in the search for ideal protective films for the practicality of AZIBs.展开更多
Aqueous zinc ion hybrid capacitors(ZIHCs)are considered one of the most promising electrochemical energy storage systems due to their high safety,environmental friendliness,low cost,and high power density.However,the ...Aqueous zinc ion hybrid capacitors(ZIHCs)are considered one of the most promising electrochemical energy storage systems due to their high safety,environmental friendliness,low cost,and high power density.However,the low energy density and the lack of sustainable design strategies for the cathodes hinder the practical application of ZIHCs.Herein,we design the N and O co-doped porous carbon cathode by annealing metal-organic framework(ZIF-8).ZIF-8 retains the original dodecahedral structure with a high specific surface(2814.67 m^(2)/g)and I_(G)/I_(D) ratio of 1.0 during carbonization and achieves self-doping of N and O heteroatoms.Abundant defect sites are introduced into the porous carbon to provide additional active sites for ion adsorption after the activation of carbonized ZIF-8 by KOH treatment.The ZIHCs assembled with modified ZIF-8 as the cathode and commercial zinc foil as the anode show an energy density of 125 W∙h/kg and a power density of 79 W/kg.In addition,this ZIHCs device achieves capacity retention of 77.8%after 9000 electrochemical cycles,which is attributed to the diverse pore structure and plentiful defect sites of ZIF-8-800(KOH).The proposed strategy may be useful in developing high-performance metal-ion hybrid capacitors for large-scale energy storage.展开更多
Octahedral Mn_(3)O_(4)nanoparticles with an Ag-doping and nanoporous Ag(NPS)framework was simply fabricated through an alloying-etching engineering.The dual-modified Mn_(3)O_(4)(denoted as Ag−Mn_(3)O_(4)/NPS)consists ...Octahedral Mn_(3)O_(4)nanoparticles with an Ag-doping and nanoporous Ag(NPS)framework was simply fabricated through an alloying-etching engineering.The dual-modified Mn_(3)O_(4)(denoted as Ag−Mn_(3)O_(4)/NPS)consists of Ag-doped Mn_(3)O_(4)nanoparticles crosslinked with three dimensional nanoporous Ag framework.The incorporated Ag dopant is effective in improving the intrinsic ionic and electronic conductivities of Mn_(3)O_(4),while the NPS framework is introduced to improve the electron/mass transfer across the entire electrode.Profiting from the dual-modification strategy,the Ag−Mn_(3)O_(4)/NPS exhibits admirable rate capability and cycling stability.A high reversible capacity of 88.7 mA·h/g can still be retained for over 1000 cycles at a current density of 1 A/g.Moreover,a series of ex-situ experimental techniques indicate that for Ag−Mn_(3)O_(4)/NPS electrode during the zinc ion storage,Mn_(3)O_(4)is electrochemically oxidized into various MnOx(e.g.,Mn_(2)O_(3),MnO2)species in the initial charging,and the subsequent battery reaction is actually the intercalation/deintercalation of H+and Zn2+into MnOx.展开更多
V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)i...V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)intercalated VO with nanoribbon structure was prepared by a simple in-situ pre-intercalation,which is noted VO-PPyd.The total density of states(TDOS)shows that after the pre-intercalation of PPyd,an intermediate energy level appears between the valence band and conduction band,which provides a step that can effectively reduce the band gap and enhance the electron conductivity.Furthermore,the density functional theory(DFT)results found that Zn^(2+)is more easily de-intercalated from the V-O skeleton,which proves that the embeddedness of PPyd improves the diffusion kinetics of Zn^(2+).Electrochemical studies have shown that VO-PPyd cathode materials exhibit excellent rate performance(high specific capacity of 465 and 192 mA h g^(-1)at 0.2 and 10 A g^(-1),respectively)and long-term cycling performance(92.7%capacity retention rate after 5300 cycles),due to their advantages in structure and composition.More importantly,the energy density of VO-PPyd//Zn at 581 and 5806 W kg^(-1)is 375 and 247 W h kg^(-1),respectively.VO-PPyd exhibits excellent electrochemical properties compared to previously reported vanadium based cathodes,which makes it highly competitive in the field of high-performance cathode materials of AZIBs.展开更多
A conventional electrode composite for rechargeable zinc-ion batteries(ZIBs)includes a binder for strong adhesion between the electrode material and the current collector.However,the introduction of a binder leads to ...A conventional electrode composite for rechargeable zinc-ion batteries(ZIBs)includes a binder for strong adhesion between the electrode material and the current collector.However,the introduction of a binder leads to electrochemical inactivity and low electrical conductivity,resulting in the decay of the capacity and a low rate capability.We present a binder-and conducting agent-free VO_(2) composite electrode using in situ polymerization of dopamine on a flexible current collector of pyroprotein-based fibers.The as-fabricated composite electrode was used as a substrate for the direct growth of VO_(2) as a self-supported form on polydopamine-derived pyroprotein-based fibers(pp-fibers@VO_(2)(B)).It has a high conductivity and flexible nature as a current collector and moderate binding without conventional binders and conducting agents for the VO_(2)(B) cathode.In addition,their electrochemical mechanism was elucidated.Their energy storage is induced by Zn^(2+)/H^(+) coinsertion during discharging,which can be confirmed by the lattice expansion,the formation of by-products including Zn_(x)(OTf)_(y)(OH)_(2x−y)·nH_(2)O,and the reduction of V^(4+)to V^(3+).Furthermore,the assembled Zn//pp-fibers@VO_(2)(B) pouch cells have excellent flexibility and stable electrochemical performance under various bending states,showing application possibilities for portable and wearable power sources.展开更多
The increasing demands for environmentally friendly grid-scale electric energy storage devices with high energy density and low cost have stimulated the rapid development of various energy storage systems,due to the e...The increasing demands for environmentally friendly grid-scale electric energy storage devices with high energy density and low cost have stimulated the rapid development of various energy storage systems,due to the environmental pollution and energy crisis caused by traditional energy storage technologies.As one of the new and most promising alternative energy storage technologies,zinc-ion rechargeable batteries have recently received much attention owing to their high abundance of zinc in natural resources,intrinsic safety,and cost effectiveness,when compared with the popular,but unsafe and expensive lithium-ion batteries.In particular,the use of mild aqueous electrolytes in zinc-ion batteries(ZIBs)demonstrates high potential for portable electronic applications and large-scale energy storage systems.Moreover,the development of superior electrolyte operating at either high temperature or subzero condition is crucial for practical applications of ZIBs in harsh environments,such as aerospace,airplanes,or submarines.However,there are still many existing challenges that need to be resolved.This paper presents a timely review on recent progresses and challenges in various cathode materials and electrolytes(aqueous,organic,and solid-state electrolytes)in ZIBs.Design and synthesis of zinc-based anode materials and separators are also briefly discussed.展开更多
In recent years,rechargeable aqueous zinc ion batteries(ZIBs),as emerging energy storage devices,stand out from numerous metal ion batteries.Due to the advantages of low cost,environmentally friendly characteristic an...In recent years,rechargeable aqueous zinc ion batteries(ZIBs),as emerging energy storage devices,stand out from numerous metal ion batteries.Due to the advantages of low cost,environmentally friendly characteristic and safety,ZIBs can be considered as alternatives to lithium-ion batteries(LIBs).Vanadiumbased compounds with various structures and large layer spacings are considered as suitable cathode candidates for ZIBs.In this review,the recent research advances of vanadium-based electrode materials are systematically summarized.The electrode design strategy,electrochemical performances and energy storage mechanisms are emphasized.Finally,we point out the limitation of vanadium-based materials at present and the future prospect.展开更多
The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechar...The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechargeable ZIBs possess merits of high security,low cost,environmental friendliness,and competitive performance,and they are received a lot of attention.However,the development of suitable zinc ion intercalation-type cathode materials is still a big challenge,resulting in failing to meet the commercial needs of ZIBs.Both vanadium-based and manganese-based compounds are representative of the most advanced and most widely used rechargeable ZIBs electrodes.The valence state of vanadium is+2~+5,which can realize multi-electron transfer in the redox reaction and has a high specific capacity.Most of the manganese-based compounds have tunnel structure or three-dimensional space frame,with enough space to accommodate zinc ions.In order to understand the energy storage mechanism and electrochemical performance of these two materials,a specialized review focusing on state-of-the-art developments is needed.This review offers access for researchers to keep abreast of the research progress of cathode materials for ZIBs.The latest advanced researches in vanadium-based and manganese-based cathode materials applied in aqueous ZIBs are highlighted.This article will provide useful guidance for future studies on cathode materials and aqueous ZIBs.展开更多
Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,th...Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,the under-debate proton reaction mechanism and unsatisfactory electrochemical performance limit their applications.Nanorod b-MnO_(2) synthesized by hydrothermal method is used to investigate the reaction mechanism.As cathode materials for RAZIB,the Zn//b-MnO_(2) delivers 355 mA h g^(-1)(based on cathode mass)at0.1 A g^(-1),and retain 110 mA h g^(-1) after 1000 cycles at 0.2 A g^(-1).Different from conventional zinc ion insertion/extraction mechanism,the proton conversion and Mn ion dissolution/deposition mechanism of b-MnO_(2) is proposed by analyzing the evolution of phase,structure,morphology,and element of b-MnO_(2) electrode,the pH change of electrolyte and the determination of intermediate phase MnO OH.Zinc ion,as a kind of Lewis acid,also provides protons through the formation of ZHS in the proton reaction process.This study of reaction mechanism provides a new perspective for the development of Zn//MnO_(2) battery chemistry.展开更多
Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrin...Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrinsically poor rate performance and rapid capacity deterioration.Here,we remove the roadblock by compositing MnO2 nanorods with highly conductive graphene,which remarkably enhances the electrochemical properties of the MnO2 cathode.Benefiting from the boosted electric conductivity and ion diffusion rate as well as the structural protection of graphene,the Zn//MnO2-graphene battery presents an admirable capacity of 301 mAh g^-1 at 0.5 A g^-1,corresponding to a high energy density of 411.6 Wh kg^-1.Even at a high current density of 10 A g^-1,a decent capacity of 95.8 mAh g^-1 is still obtained,manifesting its excellent rate property.Furthermore,an impressive power density of 15 kW kg^-1 is achieved by the Zn//MnO2-graphene battery.展开更多
Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most impor...Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most important cathode materials of ZIB.In this paper,α-Mn2O3 used as cathode of ZIB is synthesized via Metal-Organic Framework(MOF)-derived method,which delivers a high specific capacity of225 mAh g^(-1) at 0.05 A g^(-1) and 92.7 mAh g^(-1) after 1700 cycles at 2 A g^(-1).The charge storage mechanism of α-Mn2O3 cathode is found to greatly depend on the discharge current density.At lower current density discharging,the H+ and Zn2+ are successively intercalated into the α-Mn2O3 before and after the "turning point" of discharge voltage and their discharging products present obviously different morphologies changing from flower-like to large plate-like products.At a higher current density,the low-voltage plateau after the turning point disappears due to the decrease of amount of Zn2+ intercalation and the H+intercalation is dominated in α-Mn2 O3.This study provides significant understanding for future design and research of high-performance Mn-based cathodes of ZIB.展开更多
Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applic...Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.展开更多
基金funds from the National Natural Science Foundation of China(51772082 and 51804106)the Natural Science Foundation of Hunan Province(2023JJ10005)
文摘Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097,22304055)the Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+4 种基金the Youth Talent Program of Hebei Provincial Education Department(BJ2018020)the Natural Science Foundation of Hebei Province(E2020209151,E2022209158,B2022209026,D2023209012)the Central Guiding Local Science and Technology Development Fund Project(236Z4409G)the Science and Technology Project of Hebei Education Department(SLRC2019028)the Science and Technology Planning Project of Tangshan City(22130227H)。
文摘With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.
基金supported by the National Natural Science Foundation of China(52174247 and 22302066)“Hejian”Innovative Talent Project of Hunan Province(No.2022RC1088)+1 种基金the Hunan Provincial Natural Science Foundation(2023JJ40255)the Scientific Research Foundation of Hunan Provincial Education(22B0599 and 23A0442)。
文摘Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.
基金financially supported by the National Natural Science Foundation of China (Nos.51872090 and51772097)the Hebei Natural Science Fund for Distinguished Young Scholar,China (No.E2019209433)+2 种基金the Youth Talent Program of Hebei Provincial Education Department,China (No.BJ2018020)the Natural Science Foundation of Hebei Province,China (No.E2020209151)the Science and Technology Project of Hebei Education Department,China (No.SLRC2019028)。
文摘Zinc-ion batteries(ZIBs) are recognized as potential energy storage devices due to their advantages of low cost, high energy density, and environmental friendliness. However, zinc anodes are subject to unavoidable zinc dendrites, passivation, corrosion, and hydrogen evolution reactions during the charging and discharging of batteries, becoming obstacles to the practical application of ZIBs. Appropriate zinc metal-free anodes provide a higher working potential than metallic zinc anodes, effectively solving the problems of zinc dendrites, hydrogen evolution, and side reactions during the operation of metallic zinc anodes. The improvement in the safety and cycle life of batteries creates conditions for further commercialization of ZIBs. Therefore, this work systematically introduces the research progress of zinc metal-free anodes in “rocking chair” ZIBs. Zinc metal-free anodes are mainly discussed in four categories: transition metal oxides,transition metal sulfides, MXene(two dimensional transition metal carbide) composites, and organic compounds, with discussions on their properties and zinc storage mechanisms. Finally, the outlook for the development of zinc metal-free anodes is proposed. This paper is expected to provide a reference for the further promotion of commercial rechargeable ZIBs.
基金financially supported by National Natural Science Foundation of China(No.82204604,22304055)Youth Talent Program of Hebei Provincial Education Department(No.BJ2018020)+1 种基金Natural Science Foundation of Hebei Province(No.E2020209151,E2022209158,H2022209012)Science and Technology Project of Hebei Education Department(No.JZX2024026)。
文摘Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.
基金supported financially by the Natural Science Foundation of Shandong Province,China(grant numbers ZR2020QE067,ZR2020QB117,and ZR2022MB143)the New Colleges and Universities Twenty Foundational Projects of Jinan City,China(grant number 2021GXRC068)+2 种基金the National Natural Science Foundation of China,China(grant number 22208174)The Scientific Research Foundation in Qilu University of Technology(Shandong Academy of Sciences),China(grant numbers 2023PY002)The Talent research project of Qilu University of Technology(Shandong Academy of Sciences),China(grant numbers 2023RCKY013)。
文摘Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high electrochemical performance owing to the limited electronic conductivity,sluggish ion kinetics,and severe volume expansion during the insertion/extraction process of Zn^(2+).Herein,a series of V_(2)O_(3)nanospheres embedded N-doped carbon nanofiber structures with various V_(2)O_(3)spherical morphologies(solid,core-shell,hollow)have been designed for the first time by an electrospinning technique followed thermal treatments.The N-doped carbon nanofibers not only improve the electrical conductivity and the structural stability,but also provides encapsulating shells to prevent the vanadium dissolution and aggregation of V_(2)O_(3)particles.Furthermore,the varied morphological structures of V_(2)O_(3)with abundant oxygen vacancies can alleviate the volume change and increase the Zn^(2+)pathway.Besides,the phase transition between V_(2)O_(3)and Zn_XV_(2)O_(5-m)·n H_(2)O in the cycling was also certified.As a result,the as-obtained composite delivers excellent long-term cycle stability and enhanced rate performance for coin cells,which is also confirmed through density functional theory(DFT)calculations.Even assembled into flexible ZIBs,the sample still exhibits superior electrochemical performance,which may afford new design concept for flexible cathode materials of ZIBs.
基金the financial support from the National Key Research and Development Program of China(2022YFA1207503)the Giga Force Electronics Interdisciplinary Funding(JJHXM002208-2023)。
文摘Exploring suitable high-capacity V_(2)O_(5)-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries(ZIBs).However,the typical problem of slow Zn^(2+)diffusion kinetics has severely limited the feasibility of such materials.In this work,unique hydrated vanadates(CaVO,BaVO)were obtained by intercalation of Ca^(2+)or Ba^(2+)into hydrated vanadium pentoxide.In the CaVO//Zn and BaVO//Zn batteries systems,the former delivered up to a 489.8 mAh g^(-1)discharge specific capacity at 0.1 A g^(-1).Moreover,the remarkable energy density of 370.07 Wh kg^(-1)and favorable cycling stability yard outperform BaVO,pure V_(2)O_(5),and many reported cathodes of similar ionic intercalation compounds.In addition,pseudocapacitance analysis,galvanostatic intermittent titration(GITT)tests,and Trasatti analysis revealed the high capacitance contribution and Zn^(2+)diffusion coefficient of CaVO,while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO.Notably,ex-situ XRD,XPS,and TEM tests further demonstrated the Zn^(2+)insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system.This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.
基金financially supported by National Natural Science Foundation of China(No.52102270)the Natural Science Foundation of Shandong Province of China(ZR2021QE002)+1 种基金the support from the Institute startup grant from Qingdao Universitythe Shandong Center for Engineered Nonwovens(SCEN)。
文摘Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.
基金supported by the National Natural Science Foundation of China (52373065)the Joint Fund of Ministry of Education for Equipment Pre-research (8091B032206)+1 种基金the Guang Dong Basic and Applied Basic Research Foundation (2021A1515111067,2023A1515010735)the start-up funding of“Hundred Talent Program”from Sun Yat-sen University。
文摘The notorious growth of zinc dendrite and the water-induced corrosion of zinc metal anodes(ZMAs)restrict the practical development of aqueous zinc ion batteries(AZIBs).In this work,a zinc metallized,imide-pillared covalent organic framework(ZPC)protective film has been engineered as a stable Zn^(2+)ion-conducting interphase to modulate interfacial kinetics and suppress side reactions for ZMAs.Compared to bare Zn,ZPC@Zn exhibits a higher Zn^(2+)ionic conductivity,a larger Zn^(2+)transference number,a lower electronic conductivity,a smaller desolvation activation energy and correspondingly a significant suppression of corrosion,hydrogen evolution and Zn dendrites.Impressively,the ZPC@Zn||ZPC@Zn symmetric cell obtains a cycling lifespan over 3000 h under 5 mA cm^(-2)for 1 mA h cm^(-2).The ZPC@Zn||NH_(4)V_(4)O_(10)coin-type full battery delivers a specific capacity of 195.8 mA h g^(-1)with a retention rate of78.5%at 2 A g^(-1)after 1100 cycles,and the ZPC@Zn||NH_(4)V_(4)O_(10) pouch full cell shows a retention of70.1%in reversible capacity at 3 A g^(-1)after 1100 cycles.The present incorporation of imide-linked covalent organic frameworks in the surface modification of ZMAs will offer fresh perspectives in the search for ideal protective films for the practicality of AZIBs.
基金Project(22109181)supported by the National Natural Science Foundation of ChinaProject(2022JJ40576)supported by the Hunan Provincial Natural Science Foundation of China。
文摘Aqueous zinc ion hybrid capacitors(ZIHCs)are considered one of the most promising electrochemical energy storage systems due to their high safety,environmental friendliness,low cost,and high power density.However,the low energy density and the lack of sustainable design strategies for the cathodes hinder the practical application of ZIHCs.Herein,we design the N and O co-doped porous carbon cathode by annealing metal-organic framework(ZIF-8).ZIF-8 retains the original dodecahedral structure with a high specific surface(2814.67 m^(2)/g)and I_(G)/I_(D) ratio of 1.0 during carbonization and achieves self-doping of N and O heteroatoms.Abundant defect sites are introduced into the porous carbon to provide additional active sites for ion adsorption after the activation of carbonized ZIF-8 by KOH treatment.The ZIHCs assembled with modified ZIF-8 as the cathode and commercial zinc foil as the anode show an energy density of 125 W∙h/kg and a power density of 79 W/kg.In addition,this ZIHCs device achieves capacity retention of 77.8%after 9000 electrochemical cycles,which is attributed to the diverse pore structure and plentiful defect sites of ZIF-8-800(KOH).The proposed strategy may be useful in developing high-performance metal-ion hybrid capacitors for large-scale energy storage.
基金financially supported by the Natural Science Foundation of Shandong Province,China (Nos.ZR2023ME155,ZR2023ME085)the National Natural Science Foundation of China (No.52201254)+1 种基金the Project of“20 Items of University”of Jinan,China (No.202228046)the Taishan Scholar Project of Shandong Province,China (No.tsqn202306226)。
文摘Octahedral Mn_(3)O_(4)nanoparticles with an Ag-doping and nanoporous Ag(NPS)framework was simply fabricated through an alloying-etching engineering.The dual-modified Mn_(3)O_(4)(denoted as Ag−Mn_(3)O_(4)/NPS)consists of Ag-doped Mn_(3)O_(4)nanoparticles crosslinked with three dimensional nanoporous Ag framework.The incorporated Ag dopant is effective in improving the intrinsic ionic and electronic conductivities of Mn_(3)O_(4),while the NPS framework is introduced to improve the electron/mass transfer across the entire electrode.Profiting from the dual-modification strategy,the Ag−Mn_(3)O_(4)/NPS exhibits admirable rate capability and cycling stability.A high reversible capacity of 88.7 mA·h/g can still be retained for over 1000 cycles at a current density of 1 A/g.Moreover,a series of ex-situ experimental techniques indicate that for Ag−Mn_(3)O_(4)/NPS electrode during the zinc ion storage,Mn_(3)O_(4)is electrochemically oxidized into various MnOx(e.g.,Mn_(2)O_(3),MnO2)species in the initial charging,and the subsequent battery reaction is actually the intercalation/deintercalation of H+and Zn2+into MnOx.
基金supported by the National Natural Science Foundation of China (21676036)the Natural Science Foundation of Chongqing (CSTB2023NSCQ-MSX0580)the Graduate Research and Innovation Foundation of Chongqing (CYB22043 and CYS22073)。
文摘V_(3)O_(7)·H_(2)O(VO)is a high capacity cathode material in the field of aqueous zinc ion batteries(AZIBs),but it is limited by slow ion migration and low electrical conductivity.In this paper,polypyridine(PPyd)intercalated VO with nanoribbon structure was prepared by a simple in-situ pre-intercalation,which is noted VO-PPyd.The total density of states(TDOS)shows that after the pre-intercalation of PPyd,an intermediate energy level appears between the valence band and conduction band,which provides a step that can effectively reduce the band gap and enhance the electron conductivity.Furthermore,the density functional theory(DFT)results found that Zn^(2+)is more easily de-intercalated from the V-O skeleton,which proves that the embeddedness of PPyd improves the diffusion kinetics of Zn^(2+).Electrochemical studies have shown that VO-PPyd cathode materials exhibit excellent rate performance(high specific capacity of 465 and 192 mA h g^(-1)at 0.2 and 10 A g^(-1),respectively)and long-term cycling performance(92.7%capacity retention rate after 5300 cycles),due to their advantages in structure and composition.More importantly,the energy density of VO-PPyd//Zn at 581 and 5806 W kg^(-1)is 375 and 247 W h kg^(-1),respectively.VO-PPyd exhibits excellent electrochemical properties compared to previously reported vanadium based cathodes,which makes it highly competitive in the field of high-performance cathode materials of AZIBs.
基金supported by“Regional Innovation Strategy (RIS)”through the National Research Foundation of Korea (NRF)funded by the Ministry of Education (MOE) (2021RIS-001)supported by National Research Foundation (NRF)funded by the Ministry of Science and Technology (NRF-2021R1F1A1064111)Ministry of Education (NRF-2017R1A6A1A06015181)of the Republic of Korea.
文摘A conventional electrode composite for rechargeable zinc-ion batteries(ZIBs)includes a binder for strong adhesion between the electrode material and the current collector.However,the introduction of a binder leads to electrochemical inactivity and low electrical conductivity,resulting in the decay of the capacity and a low rate capability.We present a binder-and conducting agent-free VO_(2) composite electrode using in situ polymerization of dopamine on a flexible current collector of pyroprotein-based fibers.The as-fabricated composite electrode was used as a substrate for the direct growth of VO_(2) as a self-supported form on polydopamine-derived pyroprotein-based fibers(pp-fibers@VO_(2)(B)).It has a high conductivity and flexible nature as a current collector and moderate binding without conventional binders and conducting agents for the VO_(2)(B) cathode.In addition,their electrochemical mechanism was elucidated.Their energy storage is induced by Zn^(2+)/H^(+) coinsertion during discharging,which can be confirmed by the lattice expansion,the formation of by-products including Zn_(x)(OTf)_(y)(OH)_(2x−y)·nH_(2)O,and the reduction of V^(4+)to V^(3+).Furthermore,the assembled Zn//pp-fibers@VO_(2)(B) pouch cells have excellent flexibility and stable electrochemical performance under various bending states,showing application possibilities for portable and wearable power sources.
基金the Economic Development Assistantship and the Research Enhancement Awards program sponsored by LaSPACE for financial support.
文摘The increasing demands for environmentally friendly grid-scale electric energy storage devices with high energy density and low cost have stimulated the rapid development of various energy storage systems,due to the environmental pollution and energy crisis caused by traditional energy storage technologies.As one of the new and most promising alternative energy storage technologies,zinc-ion rechargeable batteries have recently received much attention owing to their high abundance of zinc in natural resources,intrinsic safety,and cost effectiveness,when compared with the popular,but unsafe and expensive lithium-ion batteries.In particular,the use of mild aqueous electrolytes in zinc-ion batteries(ZIBs)demonstrates high potential for portable electronic applications and large-scale energy storage systems.Moreover,the development of superior electrolyte operating at either high temperature or subzero condition is crucial for practical applications of ZIBs in harsh environments,such as aerospace,airplanes,or submarines.However,there are still many existing challenges that need to be resolved.This paper presents a timely review on recent progresses and challenges in various cathode materials and electrolytes(aqueous,organic,and solid-state electrolytes)in ZIBs.Design and synthesis of zinc-based anode materials and separators are also briefly discussed.
基金supported by the Open Project Program of Wuhan National Laboratory for Optoelectronics(No.2019WNLOKF017)Education Department Funding of Liaoning province(LJGD2019001)Funding of Science and Technology Bureau,Shenyang City(No.RC190138)。
文摘In recent years,rechargeable aqueous zinc ion batteries(ZIBs),as emerging energy storage devices,stand out from numerous metal ion batteries.Due to the advantages of low cost,environmentally friendly characteristic and safety,ZIBs can be considered as alternatives to lithium-ion batteries(LIBs).Vanadiumbased compounds with various structures and large layer spacings are considered as suitable cathode candidates for ZIBs.In this review,the recent research advances of vanadium-based electrode materials are systematically summarized.The electrode design strategy,electrochemical performances and energy storage mechanisms are emphasized.Finally,we point out the limitation of vanadium-based materials at present and the future prospect.
基金financially supported by the National Natural Science Foundation of China(No.51872090,51772097)the Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433,E2017209079)the financial support from Hunan Provincial Science and Technology Plan Project of China(No.2016TP1007,2017TP1001,and 2018RS3009)。
文摘The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechargeable ZIBs possess merits of high security,low cost,environmental friendliness,and competitive performance,and they are received a lot of attention.However,the development of suitable zinc ion intercalation-type cathode materials is still a big challenge,resulting in failing to meet the commercial needs of ZIBs.Both vanadium-based and manganese-based compounds are representative of the most advanced and most widely used rechargeable ZIBs electrodes.The valence state of vanadium is+2~+5,which can realize multi-electron transfer in the redox reaction and has a high specific capacity.Most of the manganese-based compounds have tunnel structure or three-dimensional space frame,with enough space to accommodate zinc ions.In order to understand the energy storage mechanism and electrochemical performance of these two materials,a specialized review focusing on state-of-the-art developments is needed.This review offers access for researchers to keep abreast of the research progress of cathode materials for ZIBs.The latest advanced researches in vanadium-based and manganese-based cathode materials applied in aqueous ZIBs are highlighted.This article will provide useful guidance for future studies on cathode materials and aqueous ZIBs.
基金the financial supports from International Science&Technology Cooperation Program of China(No.2016YFE0102200)Shenzhen Technical Plan Project(No.JCYJ20160301154114273)+1 种基金National Key Basic Research(973)Program of China(No.2014CB932400)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01N111)。
文摘Rechargeable aqueous zinc ion battery(RAZIB)is a promising energy storage system due to its high safety,and high capacity.Among them,manganese oxides with low cost and low toxicity have drawn much attention.However,the under-debate proton reaction mechanism and unsatisfactory electrochemical performance limit their applications.Nanorod b-MnO_(2) synthesized by hydrothermal method is used to investigate the reaction mechanism.As cathode materials for RAZIB,the Zn//b-MnO_(2) delivers 355 mA h g^(-1)(based on cathode mass)at0.1 A g^(-1),and retain 110 mA h g^(-1) after 1000 cycles at 0.2 A g^(-1).Different from conventional zinc ion insertion/extraction mechanism,the proton conversion and Mn ion dissolution/deposition mechanism of b-MnO_(2) is proposed by analyzing the evolution of phase,structure,morphology,and element of b-MnO_(2) electrode,the pH change of electrolyte and the determination of intermediate phase MnO OH.Zinc ion,as a kind of Lewis acid,also provides protons through the formation of ZHS in the proton reaction process.This study of reaction mechanism provides a new perspective for the development of Zn//MnO_(2) battery chemistry.
基金financially supported by the Guangdong Power Grid Co.,Ltd.(Grant No.GDKJXM20160000)。
文摘Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrinsically poor rate performance and rapid capacity deterioration.Here,we remove the roadblock by compositing MnO2 nanorods with highly conductive graphene,which remarkably enhances the electrochemical properties of the MnO2 cathode.Benefiting from the boosted electric conductivity and ion diffusion rate as well as the structural protection of graphene,the Zn//MnO2-graphene battery presents an admirable capacity of 301 mAh g^-1 at 0.5 A g^-1,corresponding to a high energy density of 411.6 Wh kg^-1.Even at a high current density of 10 A g^-1,a decent capacity of 95.8 mAh g^-1 is still obtained,manifesting its excellent rate property.Furthermore,an impressive power density of 15 kW kg^-1 is achieved by the Zn//MnO2-graphene battery.
基金supported by the National Natural Science Foundation of China (51672156)Local Innovative Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01N111)+2 种基金Guangdong Province Technical Plan Project (2017B010119001)Shenzhen Technical Plan Project (JCYJ20170817161221958 and JCYJ20170412170706047)Shenzhen Graphene Manufacturing Innovation Center (201901161513)。
文摘Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most important cathode materials of ZIB.In this paper,α-Mn2O3 used as cathode of ZIB is synthesized via Metal-Organic Framework(MOF)-derived method,which delivers a high specific capacity of225 mAh g^(-1) at 0.05 A g^(-1) and 92.7 mAh g^(-1) after 1700 cycles at 2 A g^(-1).The charge storage mechanism of α-Mn2O3 cathode is found to greatly depend on the discharge current density.At lower current density discharging,the H+ and Zn2+ are successively intercalated into the α-Mn2O3 before and after the "turning point" of discharge voltage and their discharging products present obviously different morphologies changing from flower-like to large plate-like products.At a higher current density,the low-voltage plateau after the turning point disappears due to the decrease of amount of Zn2+ intercalation and the H+intercalation is dominated in α-Mn2 O3.This study provides significant understanding for future design and research of high-performance Mn-based cathodes of ZIB.
基金the financial support from the National Natural Science Foundation of China (22108044)the 111 Project (B20088)+3 种基金the Fundamental Research Funds for the Central Universities (2572022DJ02)the Research and Development Program in Key Fields of Guangdong Province (2020B1111380002)the Basic Research and Applicable Basic Research in Guangzhou City (202201010290)the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery (2021GDKLPRB07)。
文摘Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.