Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and h...Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.展开更多
Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aq...Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.展开更多
Dendrites growth,chemical corrosion,and hydrogen evolution reaction(HER)on zinc anodes are the main barriers for the development of aqueous zinc-ion batteries(AZIBs).Constructing interfacial protec-tive layer is an ef...Dendrites growth,chemical corrosion,and hydrogen evolution reaction(HER)on zinc anodes are the main barriers for the development of aqueous zinc-ion batteries(AZIBs).Constructing interfacial protec-tive layer is an effective way to alleviate the side reactions on the anodes.Herein,Cu/Ti_(3)C_(2)Cl_(2)MXene(CMX)with high zincophilic and hydrophobic property is prepared by the lewis molten salts etching method,and the CMX interface protection layer is constructed by a simple spin coating.The CMX coat-ing layer can provide abundant nucleation sites and uniformize the charge distribution through the zin-cophilic Ti_(3)C_(2)Cl_(2)MXene matrix,leading to homogenous Zn deposition.In addition,the hydrophobic coat-ing contained anti-corrosive Cu nanoparticles can prevent the Zn anode from the electrolyte,beneficial for suppressing the chemical corrosion and HER.Therefore,the stable and reversible Zn plating/stripping is achieved for the Zn anode coated by the CMX,which exhibits the lifespan of over 1400 h at 0.5 mA cm^(−2),and even can steadily run for 700 h with 65 mV at 10 mA cm^(−2).Furthermore,CMX@Zn shows a high coulombic efficiency of over 100%for 3800 cycles,which indicates that the CMX@Zn electrode has excellent stability and reversibility of Zn stripping/plating.The full batteries assembled with ZnCoMnO/C(ZCM)cathodes also exhibits higher capacity(450.6 mAh g^(−1)at 0.1 A g^(−1))and cycle stability(capacity retention of 70%after 1500 cycles).This work enhanced the lifespan of AZIBs and broaden the research of multifunctional coating layer to other secondary batteries based on metal anodes.展开更多
Zinc-based aqueous rechargeable batteries have attracted extensive attention due to their low cost,safety,and environmental friendliness.However,dendrite growth and hydrogen evolution of Zn anodes limit their large-sc...Zinc-based aqueous rechargeable batteries have attracted extensive attention due to their low cost,safety,and environmental friendliness.However,dendrite growth and hydrogen evolution of Zn anodes limit their large-scale application.A new strategy to produce a polyacrylamide/reduced graphene oxide(PAM@rGO)molecular nanobrush coating and control Zn electrolyte interface engineering is proposed for use in highly reversible Zn plating/stripping.Hydrogen evolution is inhibited,and Zn deposition is consolidated using the rich zincophilic functional groups of the branched polyacrylamide chain and the high conductivity of rGO.Due to the synergistic effects of corrosion resistance and dendrite-free growth,PAM@rGO/Zn provides prolonged and reversible Zn plating/stripping.Density functional theory(DFT)calculations expand on homogenized nucleation.The PAM@rGO/Zn||activated carbon(AC)capacitor exhibits long cyclic stability,fast ion transfer,and minimal interfacial impedance.This study provides experimental and theoretical bases for the structural design of Zn anode.展开更多
Aqueous zinc-ion batteries(AZIBs)are promising contenders for energy storage systems owing to their low cost and high safety.However,their practical application is hindered by uncontrolled Zn dendrites and other side ...Aqueous zinc-ion batteries(AZIBs)are promising contenders for energy storage systems owing to their low cost and high safety.However,their practical application is hindered by uncontrolled Zn dendrites and other side reactions.Here,the three-dimensional(3D)TiO2/Cu2Se/C heterostructure layer derived from MXene/Cu-MOF is constructed on the Zn anode to control the deposition/dissolution behavior,which has numerous active sites,better electrical conductivity and excellent structural stability.Based on DFT calculation,the built-in electric field(BIEF)formed of TiO2/Cu2Se/C can enhance charge transfer and ionic diffusion to inhibit the dendrites.Furthermore,hydrophobic coating has the ability to impede the corrosion and hydrogen evolution reaction(HER)of zinc anode.Thus,TiO2/Cu2Se/C@Zn enable the stable and reversible Zn plating/stripping process with the outstanding lifetime of 1100 h at 2 mA·cm^(-2) and even 650 h at 10 mA·cm^(-2).The batteries constructed with commercial MnO2 cathodes demonstrate the remarkable capacity(248.7 mAh·g−1 at 0.1 A·g−1)and impressive cycle stability(with 71.3%capacity retention after 300 cycles).As well as extending the life of AZIBs,this study is also motivating for other metal anode based secondary batteries.展开更多
Aqueous zinc-based battery is usually plagued by serious dendrites and side reactions including Zn corrosion and water decomposition on the anode.To address the drawbacks,constructing coating layers with high conducti...Aqueous zinc-based battery is usually plagued by serious dendrites and side reactions including Zn corrosion and water decomposition on the anode.To address the drawbacks,constructing coating layers with high conductivity and anti-catalytic effects on hydrogen evolution reaction has been considered as an efficient strategy.Herein,cheap and abundant twodimensional(2D)conductive graphite(KS-6)coating layer with high electronic conductivity(~106 S·m^(−1))could directly form strong bonding with Zn foil due to high zincophilicity,which correspondingly protects Zn metal from liquid electrolyte to inhibit parasitic hydrogen evolution and guide uniform Zn electrodeposition during cycling.The KS-6 layer owns a profitable charge redistribution effect to endow Zn anode with a lower nucleation energy barrier and a more uniformly distributed electric field compared with bare Zn.Therefore,such integrated Zn anode exhibits low voltage hysteresis(~38 mV)and excellent cycling stability with dendrite-free behaviors(1 mA·cm^(−2)and 2 mAh·cm^(−2))over 2,000 h,far outperforming many reported Zn metal anodes in aqueous systems.Encouragingly,in light of the superior Zn@KS-6 anode,VNOx powders and Prussian blue analogs Mn_(2)Fe(CN)_(6)are applied as the cathode materials to assemble full batteries,which show remarkable cycling stabilities and high Coulombic efficiencies(CEs)over 200 cycles with capacity retention of 81.5%for VNOx//Zn@KS-6 battery and over 400 cycles with capacity retention of 94.6%for Mn_(2)Fe(CN)_(6)//Zn@KS-6 battery,respectively.展开更多
Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic propert...Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic property and high electrical conductivity at the same time.Herein,originating from theoretical calculation,a zincophilic particle regulation strategy is proposed to address these limitations and carbon coated Na_(3)V_(2)(PO_(4))_(3)is taken as an example to be a protective layer on zinc metal(NVPC@Zn).Na_(3)V_(2)(PO_(4))_(3)(NVP)is a common cathode material for Zn-ion batteries,which is zincophilic.Carbon materials not only offer an electron pathway to help Zn deposition onto NVPC surface,but also enhance the zinc nucleophilicity of Na_(3)V_(2)(PO_(4))_(3).Hence,this hybrid coating layer can tune zinc deposition and resist side reactions such as hydrogen generation and Zn metal corrosion.Experimentally,a symmetrical battery with NVPC@Zn electrode displays highly reversible plating/stripping behavior with a long cycle lifespan over 1800 h at2 mA cm^(-2),much better than carbon and Na_(3)V_(2)(PO_(4))_(3)solely modified Zn electrodes.When the Na_(3)V_(2)(PO_(4))_(3)is replaced with zincophobic Al2O3or zincophilic V2O3,the stability of the modified zinc anodes is also prolonged.This strategy expands the option of zincophilic materials and provides a general and effective way to stabilize the Zn electrode.展开更多
Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of ...Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.展开更多
Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hyd...Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hydrogen evolution corrosion of the Zn anode have seriously restricted the application of AZIBs.Herein,to overcome these constraints,a three-dimensional(3D)porous PFA-COOH-CNT artificial solid electrolyte interface(SEl)film with high hydrophobic and zincophilic properties was constructed on Zn anode surface by in-situ polymerization of furfuryl alcohol(FA)and carboxyl carbon nanotubes(COOH-CNT).A series of in-situ,ex-situ characterizations as well as the density functional theory(DFT)calculations reveal that the formed PFA-COOH-CNT SEI film with an abundant oxygen-containing group can provide abundant zincophilic sites and induce homogeneous deposition of Zn^(2+),as well as the hydrophobic alkyl and carbon skeleton in PFA-COOH-CNT SEI film can isolate the direct contact of H_(2)O with Zn anode,and inhibit the occurrence of hydrogen evolution reaction(HER).Accordingly,the Zn anode with PFA-COOH-CNT layer can attain an ultra-long cycle life of 2200 h at 1 mA·cm^(-2),1 mAh·cm^(-2).Simultaneously,the assembled PFA-COOH-CNT@ZnllV2Os full cell can also achieve a high reversible capacity of up to 150.2 mAh•g^(-1) at 1 A·g^(-1) after 400 cycles,with a high average coulombic efficiency(CE)of 98.8%.The designed PFA-COOH-CNT artificial SEI film provides a broad prospect for highly stable zinc anode,and can also be extended to other energy storage systems based on metal anodes.展开更多
Aqueous rechargeable zinc ion batteries are regarded as a competitive alternative to lithium-ion batteries because of their distinct advantages of high security,high energy density,low cost,and environmental friendlin...Aqueous rechargeable zinc ion batteries are regarded as a competitive alternative to lithium-ion batteries because of their distinct advantages of high security,high energy density,low cost,and environmental friendliness.However,deep-seated problems including Zn dendrite and adverse side reactions severely impede the practical application.In this work,we proposed a freestanding Zn-electrolyte interfacial layer composed of multicapsular carbon fibers(MCFs)to regulate the plating/stripping behavior of Zn anodes.The versatile MCFs protective layer can uniformize the electric field and Zn^(2+)flux,meanwhile,reduce the deposition overpotentials,leading to high-quality and rapid Zn deposition kinetics.Furthermore,the bottom-up and uniform deposition of Zn on the Zn-MCFs interface endows long-term and high-capacity plating.Accordingly,the Zn@MCFs symmetric batteries can keep working up to 1500 h with 5 mAh cm^(−2).The feasibility of the MCFs interfacial layer is also convinced in Zn@MCFs||MnO_(2) batteries.Remarkably,the Zn@MCFs||α-MnO_(2)batteries deliver a high specific capacity of 236.1 mAh g^(−1)at 1 A g^(−1)with excellent stability,and maintain an exhilarating energy density of 154.3 Wh kg^(−1) at 33%depth of discharge in pouch batteries.展开更多
Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hi...Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hindered by the sluggish desolvation kinetics at the electrode/electrolyte interface and the corresponding hydrogen evolution reaction where active water molecules tightly participate in the Zn(H_(2)O)_(6)^(2+)solvation shell.Herein,learnt from self-generated solid electrolyte interphase (SEI) in anodes,the dielectric but ion-conductive zinc niobate nanoparticles artificial layer is constructed on metallic Zn surface (ZNB@Zn),acting as a rapid desolvation promotor.The zincophilic and dielectric-conductive properties of ZNB layer accelerate interfacial desolvation/diffusion and suppress surface corrosion or dendrite formation,achieving uniform Zn plating/stripping behavior,as confirmed by electronic/optical microscopies and interface spectroscopical measurements together with theoretical calculations.Consequently,the as-prepared ZNB@Zn electrode exhibits excellent cycling stability of over 2000 h and robust reversibility (99.54%) even under high current density and depth of discharge conditions.Meanwhile,the assembled ZNB@Zn-based full cell displays high capacity-retention rate of 80.21%after 3000 cycles at 5 A g^(-1)and outstanding rate performance up to 10 A g^(-1).The large-areal pouch cell is stabilized for hundreds of cycles,highlighting the bright prospects of the dielectric but ion-conductive layer in further application of AZMBs.展开更多
Stabilizing the Zn anode under high utilization rates is highly applauded yet very challenging in aqueous Zn batteries.Here,we rationally design a zincophilic short-chain aromatic molecule,4-mercaptopyridine(4Mpy),to ...Stabilizing the Zn anode under high utilization rates is highly applauded yet very challenging in aqueous Zn batteries.Here,we rationally design a zincophilic short-chain aromatic molecule,4-mercaptopyridine(4Mpy),to construct self-assembled monolayers(SAMs)on a copper substrate to achieve highly utilized Zn anodes.We reveal that 4Mpy could be firmly bound on the Cu substrate via Cu–S bond to form compact and uniform SAMs,which could effectively isolate the water on the electrode surface and thus eliminate the water-related side reactions.In addition,the short-chain aromatic ring structure of 4Mpy could not only ensure the ordered arrangement of zincophilic pyridine N but also facilitate charge transfer,thus enabling uniform and rapid Zn deposition.Consequently,the Zn/4Mpy/Cu electrode not only enables the symmetric cell to stably cycle for over 180 h at 10 mA cm^(-2) under a high depth-of-discharge of 90%,but also allows the MnO_(2)-paired pouch cell to survive for 100 cycles under a high Zn utilization rate of 78.8%.An anode-free 4Mpy/Cu||graphite cell also operates for 150 cycles without obvious capacity fading at 0.1 A g^(-1).This control of interfacial chemistry via SAMs to achieve high utilization rates of metal anodes provides a new paradigm for developing high-energy metal-based batteries.展开更多
结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维...结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu^(2+)).在锌成核过程中,Cu^(2+)原位还原为金属Cu,然后随着锌的进一步沉积,碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层.密度泛函理论计算和实验观察表明,Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点,而且可以提高导电率,使电场和锌离子通量均匀化.因此,ACC-600@Cu^(2+)集流体可以实现高的镀锌/剥离可逆性,并在15.8 mV的极化电压下稳定循环410 h以上.作为概念验证,我们组装的Zn@ACC-600@Cu^(2+)‖MnO_(2)全电池具有良好的电池倍率性能,与原始碳布相比,其比容量显著提高至110 mA h g^(-1).本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法,促进了无枝晶和高稳定锌金属电池的发展.展开更多
基金National Natural Science Foundation of China(No.52002149)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515111202)the fellowship of China Postdoctoral Science Foundation(2020M683186)。
文摘Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.
基金partially supported by the National Natural Science Foundation of China(22479022)Liaoning Revitalization Talents Program(XLYC2007129)。
文摘Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.
基金supported by the Natural Science Foundation of China(No.51962032)the program for Strong Youth Technology Leading Talents in Bingtuan Technological Innovation Talents(No.2023CB008-11)+1 种基金the Youth Innovative Top Talents Fund,Shihezi University(No.CXBJ202203)Youth Science and Technology Innovation Leading Talent Fund,Bashi Shihezi(No.2023RC02).
文摘Dendrites growth,chemical corrosion,and hydrogen evolution reaction(HER)on zinc anodes are the main barriers for the development of aqueous zinc-ion batteries(AZIBs).Constructing interfacial protec-tive layer is an effective way to alleviate the side reactions on the anodes.Herein,Cu/Ti_(3)C_(2)Cl_(2)MXene(CMX)with high zincophilic and hydrophobic property is prepared by the lewis molten salts etching method,and the CMX interface protection layer is constructed by a simple spin coating.The CMX coat-ing layer can provide abundant nucleation sites and uniformize the charge distribution through the zin-cophilic Ti_(3)C_(2)Cl_(2)MXene matrix,leading to homogenous Zn deposition.In addition,the hydrophobic coat-ing contained anti-corrosive Cu nanoparticles can prevent the Zn anode from the electrolyte,beneficial for suppressing the chemical corrosion and HER.Therefore,the stable and reversible Zn plating/stripping is achieved for the Zn anode coated by the CMX,which exhibits the lifespan of over 1400 h at 0.5 mA cm^(−2),and even can steadily run for 700 h with 65 mV at 10 mA cm^(−2).Furthermore,CMX@Zn shows a high coulombic efficiency of over 100%for 3800 cycles,which indicates that the CMX@Zn electrode has excellent stability and reversibility of Zn stripping/plating.The full batteries assembled with ZnCoMnO/C(ZCM)cathodes also exhibits higher capacity(450.6 mAh g^(−1)at 0.1 A g^(−1))and cycle stability(capacity retention of 70%after 1500 cycles).This work enhanced the lifespan of AZIBs and broaden the research of multifunctional coating layer to other secondary batteries based on metal anodes.
基金supported by the National Natural Science Foundation of China(Nos.22208273 and 22272204)Tianchi Talent Plan of Xinjiang Uygur Autonomous Region.
文摘Zinc-based aqueous rechargeable batteries have attracted extensive attention due to their low cost,safety,and environmental friendliness.However,dendrite growth and hydrogen evolution of Zn anodes limit their large-scale application.A new strategy to produce a polyacrylamide/reduced graphene oxide(PAM@rGO)molecular nanobrush coating and control Zn electrolyte interface engineering is proposed for use in highly reversible Zn plating/stripping.Hydrogen evolution is inhibited,and Zn deposition is consolidated using the rich zincophilic functional groups of the branched polyacrylamide chain and the high conductivity of rGO.Due to the synergistic effects of corrosion resistance and dendrite-free growth,PAM@rGO/Zn provides prolonged and reversible Zn plating/stripping.Density functional theory(DFT)calculations expand on homogenized nucleation.The PAM@rGO/Zn||activated carbon(AC)capacitor exhibits long cyclic stability,fast ion transfer,and minimal interfacial impedance.This study provides experimental and theoretical bases for the structural design of Zn anode.
基金supported by the National Natural Science Foundation of China(Nos.52302105 and 51962032)the program for Strong Youth Technology Leading Talents(2023CB008-11)+2 种基金the Youth Innovative Top Talents Fund,Shihezi University(CXBJ202203)Youth Science and Technology Innovation Leading Talent Fund,Shihezi(2023RC02)Youth Innovation Promotion Association CAS(2021433).
文摘Aqueous zinc-ion batteries(AZIBs)are promising contenders for energy storage systems owing to their low cost and high safety.However,their practical application is hindered by uncontrolled Zn dendrites and other side reactions.Here,the three-dimensional(3D)TiO2/Cu2Se/C heterostructure layer derived from MXene/Cu-MOF is constructed on the Zn anode to control the deposition/dissolution behavior,which has numerous active sites,better electrical conductivity and excellent structural stability.Based on DFT calculation,the built-in electric field(BIEF)formed of TiO2/Cu2Se/C can enhance charge transfer and ionic diffusion to inhibit the dendrites.Furthermore,hydrophobic coating has the ability to impede the corrosion and hydrogen evolution reaction(HER)of zinc anode.Thus,TiO2/Cu2Se/C@Zn enable the stable and reversible Zn plating/stripping process with the outstanding lifetime of 1100 h at 2 mA·cm^(-2) and even 650 h at 10 mA·cm^(-2).The batteries constructed with commercial MnO2 cathodes demonstrate the remarkable capacity(248.7 mAh·g−1 at 0.1 A·g−1)and impressive cycle stability(with 71.3%capacity retention after 300 cycles).As well as extending the life of AZIBs,this study is also motivating for other metal anode based secondary batteries.
基金the National Key Research and Development Program of China(No.2017YFE0198100)the National Natural Science Foundation of China(No.21975250)+1 种基金the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(Nos.RERU2021004 and RERU2021006)the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,China(No.2021007).
文摘Aqueous zinc-based battery is usually plagued by serious dendrites and side reactions including Zn corrosion and water decomposition on the anode.To address the drawbacks,constructing coating layers with high conductivity and anti-catalytic effects on hydrogen evolution reaction has been considered as an efficient strategy.Herein,cheap and abundant twodimensional(2D)conductive graphite(KS-6)coating layer with high electronic conductivity(~106 S·m^(−1))could directly form strong bonding with Zn foil due to high zincophilicity,which correspondingly protects Zn metal from liquid electrolyte to inhibit parasitic hydrogen evolution and guide uniform Zn electrodeposition during cycling.The KS-6 layer owns a profitable charge redistribution effect to endow Zn anode with a lower nucleation energy barrier and a more uniformly distributed electric field compared with bare Zn.Therefore,such integrated Zn anode exhibits low voltage hysteresis(~38 mV)and excellent cycling stability with dendrite-free behaviors(1 mA·cm^(−2)and 2 mAh·cm^(−2))over 2,000 h,far outperforming many reported Zn metal anodes in aqueous systems.Encouragingly,in light of the superior Zn@KS-6 anode,VNOx powders and Prussian blue analogs Mn_(2)Fe(CN)_(6)are applied as the cathode materials to assemble full batteries,which show remarkable cycling stabilities and high Coulombic efficiencies(CEs)over 200 cycles with capacity retention of 81.5%for VNOx//Zn@KS-6 battery and over 400 cycles with capacity retention of 94.6%for Mn_(2)Fe(CN)_(6)//Zn@KS-6 battery,respectively.
基金financially supported by the National Key Research and Development Program of China(2022YFB3803600)the Fundamental Research Funds for the Central Universities(30106200463 and CCNU22CJ017)+1 种基金the National Natural Science Foundation of China(U20A20246)the Graduate Education Innovation Grant from Central China Normal University,China(20210407032)。
文摘Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic property and high electrical conductivity at the same time.Herein,originating from theoretical calculation,a zincophilic particle regulation strategy is proposed to address these limitations and carbon coated Na_(3)V_(2)(PO_(4))_(3)is taken as an example to be a protective layer on zinc metal(NVPC@Zn).Na_(3)V_(2)(PO_(4))_(3)(NVP)is a common cathode material for Zn-ion batteries,which is zincophilic.Carbon materials not only offer an electron pathway to help Zn deposition onto NVPC surface,but also enhance the zinc nucleophilicity of Na_(3)V_(2)(PO_(4))_(3).Hence,this hybrid coating layer can tune zinc deposition and resist side reactions such as hydrogen generation and Zn metal corrosion.Experimentally,a symmetrical battery with NVPC@Zn electrode displays highly reversible plating/stripping behavior with a long cycle lifespan over 1800 h at2 mA cm^(-2),much better than carbon and Na_(3)V_(2)(PO_(4))_(3)solely modified Zn electrodes.When the Na_(3)V_(2)(PO_(4))_(3)is replaced with zincophobic Al2O3or zincophilic V2O3,the stability of the modified zinc anodes is also prolonged.This strategy expands the option of zincophilic materials and provides a general and effective way to stabilize the Zn electrode.
基金supported by the Innovation Foundation of Graduate Student of Harbin Normal University (No.HSDBSCX2023-3),China。
文摘Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.
基金This study was funded by the National Natural Science Foundation of China(Nos.51902036,22222902,2263203,and 52111530236)the National Key R&D Program of China(No.2022YFA1203902)+3 种基金the Key Science and Technology Research Program of Chongqing Education Commission(No.KJZD-K202200807)the Natural Science Foundation of Chongqing Science&Technology Commission(No.CSTB2022NSCQ-MSX0828)Chongqing Bayu Scholars Support Program(No.YS2022050)Research Project of Innovative Talent Training Engineering Program of Chongqing Primary and Secondary School(No.CY240806).
文摘Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hydrogen evolution corrosion of the Zn anode have seriously restricted the application of AZIBs.Herein,to overcome these constraints,a three-dimensional(3D)porous PFA-COOH-CNT artificial solid electrolyte interface(SEl)film with high hydrophobic and zincophilic properties was constructed on Zn anode surface by in-situ polymerization of furfuryl alcohol(FA)and carboxyl carbon nanotubes(COOH-CNT).A series of in-situ,ex-situ characterizations as well as the density functional theory(DFT)calculations reveal that the formed PFA-COOH-CNT SEI film with an abundant oxygen-containing group can provide abundant zincophilic sites and induce homogeneous deposition of Zn^(2+),as well as the hydrophobic alkyl and carbon skeleton in PFA-COOH-CNT SEI film can isolate the direct contact of H_(2)O with Zn anode,and inhibit the occurrence of hydrogen evolution reaction(HER).Accordingly,the Zn anode with PFA-COOH-CNT layer can attain an ultra-long cycle life of 2200 h at 1 mA·cm^(-2),1 mAh·cm^(-2).Simultaneously,the assembled PFA-COOH-CNT@ZnllV2Os full cell can also achieve a high reversible capacity of up to 150.2 mAh•g^(-1) at 1 A·g^(-1) after 400 cycles,with a high average coulombic efficiency(CE)of 98.8%.The designed PFA-COOH-CNT artificial SEI film provides a broad prospect for highly stable zinc anode,and can also be extended to other energy storage systems based on metal anodes.
基金supported by the National Natural Science Foundation of China(51901206)“the Fundamental Research Funds for the Central Universities”(2021QNA4003).
文摘Aqueous rechargeable zinc ion batteries are regarded as a competitive alternative to lithium-ion batteries because of their distinct advantages of high security,high energy density,low cost,and environmental friendliness.However,deep-seated problems including Zn dendrite and adverse side reactions severely impede the practical application.In this work,we proposed a freestanding Zn-electrolyte interfacial layer composed of multicapsular carbon fibers(MCFs)to regulate the plating/stripping behavior of Zn anodes.The versatile MCFs protective layer can uniformize the electric field and Zn^(2+)flux,meanwhile,reduce the deposition overpotentials,leading to high-quality and rapid Zn deposition kinetics.Furthermore,the bottom-up and uniform deposition of Zn on the Zn-MCFs interface endows long-term and high-capacity plating.Accordingly,the Zn@MCFs symmetric batteries can keep working up to 1500 h with 5 mAh cm^(−2).The feasibility of the MCFs interfacial layer is also convinced in Zn@MCFs||MnO_(2) batteries.Remarkably,the Zn@MCFs||α-MnO_(2)batteries deliver a high specific capacity of 236.1 mAh g^(−1)at 1 A g^(−1)with excellent stability,and maintain an exhilarating energy density of 154.3 Wh kg^(−1) at 33%depth of discharge in pouch batteries.
基金National Key R&D Program of China (2021YFA1201503)National Natural Science Foundation of China (21972164, 22279161, 12264038, 22309144)+4 种基金Natural Science Foundation of Jiangsu Province (BK. 20210130)China Postdoctoral Science Foundation (2023M733189)Jiangsu Double-Innovation PhD Program in 2022 (JSSCBS20221241)Senior Talents Fund of Jiangsu University (5501220014)fellowship funding provided by the Alexander von Humboldt Foundation。
文摘Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety.However,their performance and sustainability are significantly hindered by the sluggish desolvation kinetics at the electrode/electrolyte interface and the corresponding hydrogen evolution reaction where active water molecules tightly participate in the Zn(H_(2)O)_(6)^(2+)solvation shell.Herein,learnt from self-generated solid electrolyte interphase (SEI) in anodes,the dielectric but ion-conductive zinc niobate nanoparticles artificial layer is constructed on metallic Zn surface (ZNB@Zn),acting as a rapid desolvation promotor.The zincophilic and dielectric-conductive properties of ZNB layer accelerate interfacial desolvation/diffusion and suppress surface corrosion or dendrite formation,achieving uniform Zn plating/stripping behavior,as confirmed by electronic/optical microscopies and interface spectroscopical measurements together with theoretical calculations.Consequently,the as-prepared ZNB@Zn electrode exhibits excellent cycling stability of over 2000 h and robust reversibility (99.54%) even under high current density and depth of discharge conditions.Meanwhile,the assembled ZNB@Zn-based full cell displays high capacity-retention rate of 80.21%after 3000 cycles at 5 A g^(-1)and outstanding rate performance up to 10 A g^(-1).The large-areal pouch cell is stabilized for hundreds of cycles,highlighting the bright prospects of the dielectric but ion-conductive layer in further application of AZMBs.
基金supported by the National Natural Science Foundation of China(22379041,52103313)National Key Research and Development Program of China(2022YFB2402400)+1 种基金The Science and Technology Innovation Program of Hunan Province(2023RC1045)Natural Science Foundation of Hunan Province(2021JJ30094).
文摘Stabilizing the Zn anode under high utilization rates is highly applauded yet very challenging in aqueous Zn batteries.Here,we rationally design a zincophilic short-chain aromatic molecule,4-mercaptopyridine(4Mpy),to construct self-assembled monolayers(SAMs)on a copper substrate to achieve highly utilized Zn anodes.We reveal that 4Mpy could be firmly bound on the Cu substrate via Cu–S bond to form compact and uniform SAMs,which could effectively isolate the water on the electrode surface and thus eliminate the water-related side reactions.In addition,the short-chain aromatic ring structure of 4Mpy could not only ensure the ordered arrangement of zincophilic pyridine N but also facilitate charge transfer,thus enabling uniform and rapid Zn deposition.Consequently,the Zn/4Mpy/Cu electrode not only enables the symmetric cell to stably cycle for over 180 h at 10 mA cm^(-2) under a high depth-of-discharge of 90%,but also allows the MnO_(2)-paired pouch cell to survive for 100 cycles under a high Zn utilization rate of 78.8%.An anode-free 4Mpy/Cu||graphite cell also operates for 150 cycles without obvious capacity fading at 0.1 A g^(-1).This control of interfacial chemistry via SAMs to achieve high utilization rates of metal anodes provides a new paradigm for developing high-energy metal-based batteries.
基金supported by the National Natural Science Foundation of China(22001236)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(19IRTSTHN022)Zhengzhou University。
文摘结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu^(2+)).在锌成核过程中,Cu^(2+)原位还原为金属Cu,然后随着锌的进一步沉积,碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层.密度泛函理论计算和实验观察表明,Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点,而且可以提高导电率,使电场和锌离子通量均匀化.因此,ACC-600@Cu^(2+)集流体可以实现高的镀锌/剥离可逆性,并在15.8 mV的极化电压下稳定循环410 h以上.作为概念验证,我们组装的Zn@ACC-600@Cu^(2+)‖MnO_(2)全电池具有良好的电池倍率性能,与原始碳布相比,其比容量显著提高至110 mA h g^(-1).本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法,促进了无枝晶和高稳定锌金属电池的发展.
