Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
Aqueous ammonium-ion batteries(AAIBs)have emerged as a promising candidate for grid-scale energy stor-age owing to their intrinsic safety(e.g.,dendrite-free and nonflammable),environmental friendliness,and potential f...Aqueous ammonium-ion batteries(AAIBs)have emerged as a promising candidate for grid-scale energy stor-age owing to their intrinsic safety(e.g.,dendrite-free and nonflammable),environmental friendliness,and potential for fast charge/discharge capability.Extensive research has been conducted in recent years to explore high-performance ammonium-ion storage materials and the associated electrochemistry to advance the commercialization of AAIBs.Therefore,it is necessary to review the progress in ammonium-ion storage materials and related electrochemical theories to guide further research on AAIBs.Herein,we systematically summarize the advanced electrode materials for AAIBs by introducing the physicochemical characteristics and ammonium-ion storage behaviors of various electrode materials,such as Prussian blue analogs,organic polymers,and metal oxides,discussing feasible material-design strategies to enhance their ammonium-ion storage performance,and outlining the future development prospects of AAIBs.This review aims to provide valuable insights into the design of advanced electrode materials for high-performance AAIBs.展开更多
The development of aqueous zinc-ion batteries is crucial for advancing sustainable energy storage technologies.However,their widespread application is hindered by Zn corrosion and uncontrolled Zn dendrite growth.One p...The development of aqueous zinc-ion batteries is crucial for advancing sustainable energy storage technologies.However,their widespread application is hindered by Zn corrosion and uncontrolled Zn dendrite growth.One promising approach involves creating a functional organic-inorganic interface on the Zn surface.Traditional binders,such as polyvinylidene fluoride(PVDF),fail to regulate water activity and ion migration,limiting the effectiveness of the interface.Herein,we introduce an aqueous dual ionic/electronic conducting binder,poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS),to build a water-scarce,Zn^(2+)-enriched interface.Our findings demonstrate that PEDOT:PSS not only facilitates uniform distribution of inorganic fillers,forming a cohesive and compact interface,but also significantly enhances mechanical integrity.Additionally,the sulfonate groups within the binder matrix disrupt the hydrogen bond network of water molecules,reducing water activity and lowering the desolvation energy barrier of Zn(H_(2)O)_(6)^(2+)clusters.Therefore,the transference number of Zn^(2+)is elevated to 0.81(compared to 0.61 with PVDF),mitigating undesirable side reactions and enabling dendrite-less Zn deposition.Consequently,symmetrical Zn||Zn cells with PEDOT:PSS binder demonstrate a lifetime with 4.2 times longer than those with PVDF.This work underscores the critical role of binder chemistry in stabilizing metal anodes for aqueous batteries.展开更多
Aqueous ion storage systems have motivated great interest by virtue of low reduction,high eco-sustainability and safety.Among various cathode candidates,transition metal compounds are featured with easy dissolution in...Aqueous ion storage systems have motivated great interest by virtue of low reduction,high eco-sustainability and safety.Among various cathode candidates,transition metal compounds are featured with easy dissolution in aqueous solutions and inferior conductivity,which severely hinder their application.Herein,advantages are taken of the“conveyor effect”of conjugated polyaniline to prepare an oxygen defective tungstate-linked polyaniline(O_(d)-WOP)material with chrysanthemum-like microstructure.By virtue of the high electronic conductivity derived from conductive conjugated polyaniline skeleton,unbalanced charge distribution triggered by the defective structure,and reversibly rapid ion(de)intercalation benefited from the open framework with porous chrysanthemum-like microstructure,it delivers outstanding rate capability with a maximum specific capacity of 162.2 mAh g^(-1)and great cycle stability for storing NH_(4)^(+).Additionally,it also adopts a high reversible capacity of 140.4 mAh g^(-1)and outstanding cycling performance to store Ca^(2+).Consequently,the assembled O_(d)-WOP//PTCDI flexible aqueous ammonium ion batteries and calcium ion batteries exhibit superior capacities,energy densities and flexibilities.O_(d)-WOP achieves the NH_(4)^(+) and Ca^(2+)storage capability by interacting with them through hydrogen and ionic bonds,respectively.The deep insight from this work sheds light upon a novel strategy to excavate greater potential of transition metal compounds for aqueous ion batteries.展开更多
Aqueous zinc-ion electrochromic(EC)technology,boasting the capability to fulfill both safety and cost-ef⁃fectiveness requirements,is garnering extensive attention in various application areas including smart windows,t...Aqueous zinc-ion electrochromic(EC)technology,boasting the capability to fulfill both safety and cost-ef⁃fectiveness requirements,is garnering extensive attention in various application areas including smart windows,thermal management,displays,and camouflage.However,typical inorganic EC materials,such as tungsten oxides(WO_(3)),of⁃ten suffer from slow ion diffusion kinetics and limited optical contrast within the aqueous Zn^(2+)electrolyte because of the large size and strong Coulombic interactions of the Zn^(2+),which limits their wide applicability.Here,ordered WO_(3)nanowire films,constructed by a one-step grazing angle deposition method,is demonstrated to boost the response speed and optical contrast during EC phenomena.Compared with dense films,the ordered WO_(3)nanowire films with a porosity of 44.6%demonstrate anti-reflective property and excellent comprehensive EC performance,including fast response time(3.6 s and 1.2 s for coloring and bleaching,respectively),large optical contrast(66.6%at 700 nm)and high col⁃oration efficiency(64.3 cm^(2)·C^(-1)).A large-area prototype EC device(17 cm×12 cm)with fast color-switching is also successfully achieved.Mechanistic studies show that the improved performance is mainly due to the ordered porous nanowire structures,which provides direct electron transfer paths and sufficient interfacial contacts,thus simultaneously enhancing the electrochemical activity and fast redox kinetics.This study provides a simple and effective strategy to im⁃prove the performance of tungsten oxide-based aqueous zinc ion EC materials and devices.展开更多
As battery technology evolves and demand for efficient energy storage solutions,aqueous zinc ion batteries(AZIBs)have garnered significant attention due to their safety and environmental benefits.However,the stability...As battery technology evolves and demand for efficient energy storage solutions,aqueous zinc ion batteries(AZIBs)have garnered significant attention due to their safety and environmental benefits.However,the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density.This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs,including hydrogen evolution reaction,phase transformation and dissolution phenomena.To address these challenges,we propose a range of advanced strategies aimed at improving the stability of cathode materials.These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions.Additionally,we emphasize the importance of designing antioxidant electrolytes,with a focus on understanding and optimizing electrolyte decomposition mechanisms.The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs.By integrating these cutting-edge approaches,this review anticipates substantial advancements in the stability of high-voltage cathode materials,paving the way for the broader application and development of AZIBs in energy storage.展开更多
Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hamp...Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hampered by the instability of both the anode-electrolyte interface and the cathode-electrolyte interface.The use of sodium gluconate(SG),an organic sodium salt with multiple hydroxyl groups,as an electrolyte additive is suggested.Experimental and theoretical analyses demonstrate that Na^(+)from SG can intercalate and deintercalate within the associated V_(2)O_(5) cathode during in situ electrochemical processes.This action supports the layered structure of V_(2)O_(5),prevents structural collapse and phase transitions,and enhances Zn^(2+)diffusion kinetics.Additionally,the gluconate anion disrupts the original Zn^(2+)solvation structure,mitigates water-induced side reactions,and suppresses Zn dendrite growth.The synchronous regulation of both the V_(2)O_(5) cathode and Zn anode by the SG additive leads to considerable performance improvements.Zn‖Zn symmetric batteries demonstrate a cycle life exceeding 2800 h at 0.5 mA cm^(-2)and 1 mAh cm^(-2).In Zn‖V_(2)O_(5) full batteries,a high specific capacity of 288.92 mAh g^(-1)and capacity retention of 82.29%are maintained over 1000 cycles at a current density of 2 A g^(-1).This multifunctional additive strategy offers a new pathway for the practical application of AZIBs.展开更多
To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoin...To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.展开更多
The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity...The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity fading and phase change of MnO_(2)-based materials in aqueous zinc ion batteries(AZIBs).Here,this study doped high valent vanadium ions into MnO_(2)(VMO-x)to inhibit manganese's Jahn-Teller effect.Through a series of characterizations,such as X-ray diffraction(XRD),Raman spectroscopy,and scanning electron microscopy(SEM),it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO_(2),facilitating the transport of ions into the interlayer.Additionally,Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)demonstrated vanadium doped could effectively adjust the electronic structure,decreasing the average oxidation state of manganese,thereby inhibiting the Jahn-Teller effect and significantly enhancing the stability of the VMO-x cathode.The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn^(2+),optimized its electron transport capacity,and led to better electrical conductivity and reaction kinetics of the VMO-5.Benefiting from this,the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79%after 2000 cycles,demonstrating excellent electrochemical performance.Furthermore,the mechanism of H^(+)/Zn^(2+)co-intercalation/deintercalation was demonstrated through mechanism analysis.Finally,the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices.This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.展开更多
Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collap...Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.展开更多
Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growt...Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.展开更多
Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials ...Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials for ASIBs,Na_(3)V_(2)(PO_(4))_(3)(NVP) exhibits excellent structural stability and a high Na+diffusion coefficient,making it a promising option.However,the high solubility of vanadium-based materials in aqueous electrolytes engenders suboptimal cycling stability for Na_(3)V_(2)(PO_(4))_(3),constraining its application in ASIBs.Herein,the Cr-substituted Na_(3)V_(1.3)Cr_(0.7)(PO_(4))3@C(NV_(1.3)Cr_(0.7)P) cathode material was synthesized via a simple sol-gel method.It is found that Cr substitution reduces the cell parameters of NV_(1.3)Cr_(0.7)P,effectively reinforcing the crystal structure.Furthermore,NV_(1.3)Cr_(0.7)P alters the Na^(+)insertion/extraction mechanism,transforming the typical two-phase reaction between Na_(1)V_(2)(PO_(4))_(3)and Na_(3)V_(2)(PO_(4))3into continuous solid-solution reactions with stable intermediates.The Cr substitution diminishes the sodium-ion diffusion energy barrier in NV_(1.3)Cr_(0.7)P,leading to smoother Na+insertion and extraction processes.Consequently,NV_(1.3)Cr_(0.7)P exhibits impressive cycling stability,retaining 74.8% of its capacity after 5,000 cycles at a current density of 5 A g^(-1),along with an outstanding rate performance of 79,2% at 10 A g^(-1).This work elucidates the stable Na^(+)insertion/extraction processes in Cr-substituted NV_(1.3)Cr_(0.7)P,offering insights into the application of vanadium-based materials in aqueous sodium-ion batteries.展开更多
V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve th...V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.展开更多
Aqueous organic redox flow batteries(AORFBs)exploit the reversible electrochemical reactions of watersoluble organic redox-active species to store electricity and have emerged as promising electrochemical energy stora...Aqueous organic redox flow batteries(AORFBs)exploit the reversible electrochemical reactions of watersoluble organic redox-active species to store electricity and have emerged as promising electrochemical energy storage technologies.To improve the battery performance related to the cell resistance,such as the power density and energy efficiency,it is essential to understand the cell resistance and determine the major contributor.Here,we conduct comprehensive electrochemical impedance spectroscopy(EIS)studies and cell polarization on a representative TEMPTMA/MV cell assembled with a commercial AMVN membrane and probe the proportion of the ohmic resistance to the total cell resistance at various stages of charge(SOCs)ranging from 10%to 100%.At 0 mA·cm^(−2),the ohmic resistance is responsible for 60.3%–71.7%of the resistance of the entire cell,whereas at high current densities(for example,when the power density reaches the maximum),the ohmic resistance still contributes 47.9%–61.4%.Our quantitative analysis highlights the dominance of the ohmic resistance and anticipates that a membrane with lower resistivity may significantly increase the power density.展开更多
For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of e...For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).展开更多
To address challenges related to the intermittency of renewable energy sources,aqueous potassium-ion batteries(AKIBs)are a promising and sustainable alternative to conventional systems for large-scale energy storage.T...To address challenges related to the intermittency of renewable energy sources,aqueous potassium-ion batteries(AKIBs)are a promising and sustainable alternative to conventional systems for large-scale energy storage.To enable their practical application,maximizing energy density and longevity while minimizing production and material costs is a key goal.In this work,we propose an AKIB consisting only of abundant and cost-efficient materials,which delivers a high energy density of more than 70 Wh kg^(-1).We combine simple strategies to stabilize the Mn-rich Prussian blue analog cathode by Fe-doping,improving the crystallinity,and tuning the electrolyte composition without employing expensive water-in-salt electrolytes.Using a mixed 2.5 M Ca(NO_(3))_(2)+1.5 M KNO_(3)electrolyte,we assemble a novel AKIB with a Fe-doped manganese hexacyanoferrate cathode and an organic poly(naphthalene-4-formylethylenediamine)anode.Besides a high energy density,the full cell delivers a specific capacity of approximately 60 mAhg^(-1),a power density of 5000 W kg^(-1),and 80% capacity retention after 600 cycles.展开更多
Aqueous sodium-ion batteries(ASIBs)have garnered significant attention as promising candidates for large-scale energy storage applications.This interest is primarily due to their abundant resource availability,environ...Aqueous sodium-ion batteries(ASIBs)have garnered significant attention as promising candidates for large-scale energy storage applications.This interest is primarily due to their abundant resource availability,environmental friendliness,cost-effectiveness,and high safety.However,their electrochemical performance is limited by the thermodynamic properties of water molecules,resulting in inadequate cycling stability and insufficient specific energy density.To address these challenges,this study developed a hydrogen-bond enhanced urea-glycerol eutectic electrolyte(UGE)to expand the electrochemical stability window(ESW)of the electrolyte and suppress corresponding side reactions.The eutectic component disrupts the original hydrogen bonding network in water,creating a new,enhanced network that reduces the activity of free water and forms a uniform,dense passivation layer on the anode.As a result,the optimized composition of UGE exhibits a broad ESW of up to 3 V(-1.44 to 1.6 V vs.Ag/AgCl).The Prussian blue(PB)/UGE/NaTi_(2)(PO_(4))_(3)@C full cell exhibits an exceptionally long lifespan of 10,000 cycles at 10 C.This study introduces a low-cost,ultra-long-life ASIB system,utilizing a green and economical eutectic electrolyte,which expands the use of eutectic electrolytes in aqueous batteries and opens a new research horizon for constructing efficient electrochemical energy storage and conversion.展开更多
High-performance aqueous zinc(Zn)-ion batteries(AZIBs)have emerged as one of the greatest favorable candidates for next-generation energy storage systems because of their low cost,sustainability,high safety,and eco-fr...High-performance aqueous zinc(Zn)-ion batteries(AZIBs)have emerged as one of the greatest favorable candidates for next-generation energy storage systems because of their low cost,sustainability,high safety,and eco-friendliness.In this report,we prepared magnesium vanadate(MgVO)-based nanostructures by a facile single-step solvothermal method with varying experimental reaction times(1,3,and 6 h)and investigated the effect of the reaction time on the morphology and layered structure for MgVO-based compounds.The newly prepared MgVO-1 h,MgVO-3 h and MgVO-6 h samples were used as cathode materials for AZIBs.Compared to the MgVO-1 h and MgVO-6 h cathodes,the MgVO-3 h cathode showed a higher specific capacity of 492.74 mA h g^(-1) at 1 A g^(-1) over 500 cycles and excellent rate behavior(291.58 mA h g^(-1) at 3.75 A g^(-1))with high cycling stability(116%)over 2000 cycles at 5 A g^(-1).Moreover,the MgVO-3 h electrode exhibited good electrochemical performance owing to its fast Zn-ion diffusion kinetics.Additionally,various ex-situ analyses confirmed that the MgVO-3 h cathode displayed excellent insertion/extraction of Zn^(2+)ions during charge and discharge processes.This study offers an efficient method for the synthesis of nanostructured MgVO-based cathode materials for high-performance AZIBs.展开更多
A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexi...A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.展开更多
Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solve...Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solvent electrolyte or additive has been widely applied to extend the lifespan of Li/Na anodes,and a similar strategy is being implemented for Zn metal electrodes.However,fluorine-containing electrolytes raise concerns regarding cost,toxicity,corrosivity,and environmental contamination.Moreover,the necessity and role of fluorine in the SEI component remain unclear,particularly in the aqueous system.Here,we report a fluorine-free inorganic-rich SEI layer in situ built by introducing a low-cost,low-concentration tetraethyl ammonium iodide(TEAI)into dilute aqueous ZnSO_(4)electrolyte.The TEAI additive is found to simultaneously modulate the Zn^(2+)solvation structure and optimize the chemisorption at the anode/electrolyte interface.The synergistic interaction between the I-/SO_(4)^(2-)anion-involved solvation structure and adsorbed TEA^(+)cations drives the formation of fluorine-free SEI with inorganics(Zn_(3)N_(2),Zn(IO_(3))_(2),Zn S,etc.),which are capable of providing fast Zn^(2+)transport ability,high-flux nucleation site,and preferential Zn(002)deposition.Besides the reductive decomposition with the formation of Irich SEI layer,the redox-active iodine species can rejuvenate inactive byproducts and dead Zn,allowing the interface self-healing and ensuring long-term interfacial stability.The TEAI-formulated electrolyte endows the Zn anode with excellent Zn reversibility by achieving dendrite-free Zn plating/stripping over 6500 h in the Zn||Zn symmetric battery at 1 mA cm^(-2).This study provides new insights into stabilizing Zn metal electrodes via robust fluorine-free interphases.展开更多
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金Guangdong Basic and Applied Basic Research Foundation(Grant No.2023A1515012087)funded by Science and Technology Projects in Guangzhou(Grant No.2024A04J3267)the Fundamental Research Funds for the Central Universities(Grant No.21624411).
文摘Aqueous ammonium-ion batteries(AAIBs)have emerged as a promising candidate for grid-scale energy stor-age owing to their intrinsic safety(e.g.,dendrite-free and nonflammable),environmental friendliness,and potential for fast charge/discharge capability.Extensive research has been conducted in recent years to explore high-performance ammonium-ion storage materials and the associated electrochemistry to advance the commercialization of AAIBs.Therefore,it is necessary to review the progress in ammonium-ion storage materials and related electrochemical theories to guide further research on AAIBs.Herein,we systematically summarize the advanced electrode materials for AAIBs by introducing the physicochemical characteristics and ammonium-ion storage behaviors of various electrode materials,such as Prussian blue analogs,organic polymers,and metal oxides,discussing feasible material-design strategies to enhance their ammonium-ion storage performance,and outlining the future development prospects of AAIBs.This review aims to provide valuable insights into the design of advanced electrode materials for high-performance AAIBs.
基金supported by the National Natural Science Foundation of China(Grant No.22461142135,22479046)the Key Programs funded by Science and Technology Department of Shaanxi Provincial Government(Grant:No.2024GX-YBXM-336)+2 种基金the Xi’an Municipal Bureau of Science and Technology(Grant:No.2023JHGXRC-0097)the Yulin Science and Technology Bureau(Grant:No.2024-CXY-161)the Xi’an Beilin District Science and Technology and Industrial Information Bureau(Grant:No.GX2440)。
文摘The development of aqueous zinc-ion batteries is crucial for advancing sustainable energy storage technologies.However,their widespread application is hindered by Zn corrosion and uncontrolled Zn dendrite growth.One promising approach involves creating a functional organic-inorganic interface on the Zn surface.Traditional binders,such as polyvinylidene fluoride(PVDF),fail to regulate water activity and ion migration,limiting the effectiveness of the interface.Herein,we introduce an aqueous dual ionic/electronic conducting binder,poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS),to build a water-scarce,Zn^(2+)-enriched interface.Our findings demonstrate that PEDOT:PSS not only facilitates uniform distribution of inorganic fillers,forming a cohesive and compact interface,but also significantly enhances mechanical integrity.Additionally,the sulfonate groups within the binder matrix disrupt the hydrogen bond network of water molecules,reducing water activity and lowering the desolvation energy barrier of Zn(H_(2)O)_(6)^(2+)clusters.Therefore,the transference number of Zn^(2+)is elevated to 0.81(compared to 0.61 with PVDF),mitigating undesirable side reactions and enabling dendrite-less Zn deposition.Consequently,symmetrical Zn||Zn cells with PEDOT:PSS binder demonstrate a lifetime with 4.2 times longer than those with PVDF.This work underscores the critical role of binder chemistry in stabilizing metal anodes for aqueous batteries.
基金supported by the Natural Science Foundation of Liaoning Province(2023-MS-115).
文摘Aqueous ion storage systems have motivated great interest by virtue of low reduction,high eco-sustainability and safety.Among various cathode candidates,transition metal compounds are featured with easy dissolution in aqueous solutions and inferior conductivity,which severely hinder their application.Herein,advantages are taken of the“conveyor effect”of conjugated polyaniline to prepare an oxygen defective tungstate-linked polyaniline(O_(d)-WOP)material with chrysanthemum-like microstructure.By virtue of the high electronic conductivity derived from conductive conjugated polyaniline skeleton,unbalanced charge distribution triggered by the defective structure,and reversibly rapid ion(de)intercalation benefited from the open framework with porous chrysanthemum-like microstructure,it delivers outstanding rate capability with a maximum specific capacity of 162.2 mAh g^(-1)and great cycle stability for storing NH_(4)^(+).Additionally,it also adopts a high reversible capacity of 140.4 mAh g^(-1)and outstanding cycling performance to store Ca^(2+).Consequently,the assembled O_(d)-WOP//PTCDI flexible aqueous ammonium ion batteries and calcium ion batteries exhibit superior capacities,energy densities and flexibilities.O_(d)-WOP achieves the NH_(4)^(+) and Ca^(2+)storage capability by interacting with them through hydrogen and ionic bonds,respectively.The deep insight from this work sheds light upon a novel strategy to excavate greater potential of transition metal compounds for aqueous ion batteries.
基金Supported by Jilin Provincial Scientific and Technological Development Program(20230508109RC,20230201051GX,20220201091GX)National Natural Science Foundation of China(62035013,61275235)。
文摘Aqueous zinc-ion electrochromic(EC)technology,boasting the capability to fulfill both safety and cost-ef⁃fectiveness requirements,is garnering extensive attention in various application areas including smart windows,thermal management,displays,and camouflage.However,typical inorganic EC materials,such as tungsten oxides(WO_(3)),of⁃ten suffer from slow ion diffusion kinetics and limited optical contrast within the aqueous Zn^(2+)electrolyte because of the large size and strong Coulombic interactions of the Zn^(2+),which limits their wide applicability.Here,ordered WO_(3)nanowire films,constructed by a one-step grazing angle deposition method,is demonstrated to boost the response speed and optical contrast during EC phenomena.Compared with dense films,the ordered WO_(3)nanowire films with a porosity of 44.6%demonstrate anti-reflective property and excellent comprehensive EC performance,including fast response time(3.6 s and 1.2 s for coloring and bleaching,respectively),large optical contrast(66.6%at 700 nm)and high col⁃oration efficiency(64.3 cm^(2)·C^(-1)).A large-area prototype EC device(17 cm×12 cm)with fast color-switching is also successfully achieved.Mechanistic studies show that the improved performance is mainly due to the ordered porous nanowire structures,which provides direct electron transfer paths and sufficient interfacial contacts,thus simultaneously enhancing the electrochemical activity and fast redox kinetics.This study provides a simple and effective strategy to im⁃prove the performance of tungsten oxide-based aqueous zinc ion EC materials and devices.
基金supported by the Exchange Program of Highend Foreign Experts of Ministry of Science and Technology of People’s Republic of China(No.G2023041003L)the Natural Science Foundation of Shaanxi Provincial Department of Education(No.23JK0367)+1 种基金the Scientific Research Startup Program for Introduced Talents of Shaanxi University of Technology(Nos.SLGRCQD2208,SLGRCQD2306,SLGRCQD2133)Contaminated Soil Remediation and Resource Utilization Innovation Team at Shaanxi University of Technology。
文摘As battery technology evolves and demand for efficient energy storage solutions,aqueous zinc ion batteries(AZIBs)have garnered significant attention due to their safety and environmental benefits.However,the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density.This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs,including hydrogen evolution reaction,phase transformation and dissolution phenomena.To address these challenges,we propose a range of advanced strategies aimed at improving the stability of cathode materials.These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions.Additionally,we emphasize the importance of designing antioxidant electrolytes,with a focus on understanding and optimizing electrolyte decomposition mechanisms.The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs.By integrating these cutting-edge approaches,this review anticipates substantial advancements in the stability of high-voltage cathode materials,paving the way for the broader application and development of AZIBs in energy storage.
基金supported by the Battery Energy Storage Testing Center of Chongqing through their provision of testing support and technical assistance。
文摘Aqueous zinc-ion batteries(AZIBs)are gaining attention owing to their affordability,high safety,and high energy density,making them a promising solution for large-scale energy storage.However,their performance is hampered by the instability of both the anode-electrolyte interface and the cathode-electrolyte interface.The use of sodium gluconate(SG),an organic sodium salt with multiple hydroxyl groups,as an electrolyte additive is suggested.Experimental and theoretical analyses demonstrate that Na^(+)from SG can intercalate and deintercalate within the associated V_(2)O_(5) cathode during in situ electrochemical processes.This action supports the layered structure of V_(2)O_(5),prevents structural collapse and phase transitions,and enhances Zn^(2+)diffusion kinetics.Additionally,the gluconate anion disrupts the original Zn^(2+)solvation structure,mitigates water-induced side reactions,and suppresses Zn dendrite growth.The synchronous regulation of both the V_(2)O_(5) cathode and Zn anode by the SG additive leads to considerable performance improvements.Zn‖Zn symmetric batteries demonstrate a cycle life exceeding 2800 h at 0.5 mA cm^(-2)and 1 mAh cm^(-2).In Zn‖V_(2)O_(5) full batteries,a high specific capacity of 288.92 mAh g^(-1)and capacity retention of 82.29%are maintained over 1000 cycles at a current density of 2 A g^(-1).This multifunctional additive strategy offers a new pathway for the practical application of AZIBs.
基金supported by the National Natural Science Foundation of China(NSFC)under Grant No.22035001 and No.52233005.
文摘To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.
基金supported the National Key Research and Development Program of China(No.2024YFA1409900)the National Natural Science Foundation of China(Nos.62101296 and 52303335)+2 种基金the China Postdoctoral Science Foundation(Nos.2021M702656 and 2023M730099)the Natural Science Foundation of Shaanxi Province(Nos.2021JQ-756 and 2021M702656)the Graduate Innovation Fund of the School of Mechanical Engineering,Shaanxi University of Technology(No.SLGJX202404)。
文摘The Jahn-Teller effect of Mn^(3+)brings drastic structural changes to MnO_(2)-based materials and accelerates the destruction and deactivation of the internal structure of the materials,thus leading to severe capacity fading and phase change of MnO_(2)-based materials in aqueous zinc ion batteries(AZIBs).Here,this study doped high valent vanadium ions into MnO_(2)(VMO-x)to inhibit manganese's Jahn-Teller effect.Through a series of characterizations,such as X-ray diffraction(XRD),Raman spectroscopy,and scanning electron microscopy(SEM),it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO_(2),facilitating the transport of ions into the interlayer.Additionally,Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)demonstrated vanadium doped could effectively adjust the electronic structure,decreasing the average oxidation state of manganese,thereby inhibiting the Jahn-Teller effect and significantly enhancing the stability of the VMO-x cathode.The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn^(2+),optimized its electron transport capacity,and led to better electrical conductivity and reaction kinetics of the VMO-5.Benefiting from this,the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79%after 2000 cycles,demonstrating excellent electrochemical performance.Furthermore,the mechanism of H^(+)/Zn^(2+)co-intercalation/deintercalation was demonstrated through mechanism analysis.Finally,the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices.This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.
基金financially supported by the National Natural Science Foundation of China(52102233)Science and Technology Project of Hebei Education Department(QN2023019)。
文摘Aqueous aluminum ion batteries(AAIBs)have garnered extensive attention due to their environmental friendliness,high theoretical capacity,and low cost.However,the sluggish reaction kinetics and severe structural collapse of the cathode material,especially manganese oxide,during the cycling process have hindered its further application.Herein,Cu^(2+)pre-interca la ted layeredδ-MnO_(2)was synthesized via a hydrothermal method.The pre-intercalated Cu^(2+)ions not only improve the conductivity of MnO_(2)cathode but also stabilize the structure to enhance stability.X-ray absorption fine structure(XAFS)combined with density functional theory(DFT)calculations confirm the formation of the covalent bond between Cu and O,increasing the electronegativity of O atoms and enhancing the H^(+)adsorption energy.Moreover,ex-situ measurements not only elucidate the Al^(3+)/H^(+)co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO_(2)cathode during cycling.This work provides a promising modification approach for the application of manganese oxides in AAIBs.
基金support from the National Natural Science Foundation of China(22209089,22178187)Natural Science Foundation of Shandong Province(ZR2022QB048,ZR2021MB006)+2 种基金Excellent Youth Science Foundation of Shandong Province(Overseas)(2023HWYQ-089)the Taishan Scholars Program of Shandong Province(tsqn201909091)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.
基金financially supported by the Scientific and Technological Plan Project of Guizhou Province ([2024]054)Additional support came from the Industry and Education Combination Innovation Platform of Intelligent Manufacturing and Graduate Joint Training Base at Guizhou University (2020-520000-83-01324061)the Guizhou Engineering Research Center for Smart Services (2203-520102-04-04-298868)。
文摘Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials for ASIBs,Na_(3)V_(2)(PO_(4))_(3)(NVP) exhibits excellent structural stability and a high Na+diffusion coefficient,making it a promising option.However,the high solubility of vanadium-based materials in aqueous electrolytes engenders suboptimal cycling stability for Na_(3)V_(2)(PO_(4))_(3),constraining its application in ASIBs.Herein,the Cr-substituted Na_(3)V_(1.3)Cr_(0.7)(PO_(4))3@C(NV_(1.3)Cr_(0.7)P) cathode material was synthesized via a simple sol-gel method.It is found that Cr substitution reduces the cell parameters of NV_(1.3)Cr_(0.7)P,effectively reinforcing the crystal structure.Furthermore,NV_(1.3)Cr_(0.7)P alters the Na^(+)insertion/extraction mechanism,transforming the typical two-phase reaction between Na_(1)V_(2)(PO_(4))_(3)and Na_(3)V_(2)(PO_(4))3into continuous solid-solution reactions with stable intermediates.The Cr substitution diminishes the sodium-ion diffusion energy barrier in NV_(1.3)Cr_(0.7)P,leading to smoother Na+insertion and extraction processes.Consequently,NV_(1.3)Cr_(0.7)P exhibits impressive cycling stability,retaining 74.8% of its capacity after 5,000 cycles at a current density of 5 A g^(-1),along with an outstanding rate performance of 79,2% at 10 A g^(-1).This work elucidates the stable Na^(+)insertion/extraction processes in Cr-substituted NV_(1.3)Cr_(0.7)P,offering insights into the application of vanadium-based materials in aqueous sodium-ion batteries.
文摘V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(22308345)the Anhui Provincial Natural Science Foundation(2308085QB68)the Fundamental Research Funds for the Central Universities(WK2060000059).
文摘Aqueous organic redox flow batteries(AORFBs)exploit the reversible electrochemical reactions of watersoluble organic redox-active species to store electricity and have emerged as promising electrochemical energy storage technologies.To improve the battery performance related to the cell resistance,such as the power density and energy efficiency,it is essential to understand the cell resistance and determine the major contributor.Here,we conduct comprehensive electrochemical impedance spectroscopy(EIS)studies and cell polarization on a representative TEMPTMA/MV cell assembled with a commercial AMVN membrane and probe the proportion of the ohmic resistance to the total cell resistance at various stages of charge(SOCs)ranging from 10%to 100%.At 0 mA·cm^(−2),the ohmic resistance is responsible for 60.3%–71.7%of the resistance of the entire cell,whereas at high current densities(for example,when the power density reaches the maximum),the ohmic resistance still contributes 47.9%–61.4%.Our quantitative analysis highlights the dominance of the ohmic resistance and anticipates that a membrane with lower resistivity may significantly increase the power density.
基金financial support from projects funded by the National Natural Science Foundation of China(52172038,22179017)the National Key Research and Development Program of China(2022YFB4101600,2022YFB4101601)。
文摘For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).
基金Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)under Germany’s Excellence Strategy-EXC 2089/1-390776260(e-conversion)for fundingfinancial support from TUM Innovation Network for Artificial Intelligence powered Multifunctional Material Design(ARTEMIS)。
文摘To address challenges related to the intermittency of renewable energy sources,aqueous potassium-ion batteries(AKIBs)are a promising and sustainable alternative to conventional systems for large-scale energy storage.To enable their practical application,maximizing energy density and longevity while minimizing production and material costs is a key goal.In this work,we propose an AKIB consisting only of abundant and cost-efficient materials,which delivers a high energy density of more than 70 Wh kg^(-1).We combine simple strategies to stabilize the Mn-rich Prussian blue analog cathode by Fe-doping,improving the crystallinity,and tuning the electrolyte composition without employing expensive water-in-salt electrolytes.Using a mixed 2.5 M Ca(NO_(3))_(2)+1.5 M KNO_(3)electrolyte,we assemble a novel AKIB with a Fe-doped manganese hexacyanoferrate cathode and an organic poly(naphthalene-4-formylethylenediamine)anode.Besides a high energy density,the full cell delivers a specific capacity of approximately 60 mAhg^(-1),a power density of 5000 W kg^(-1),and 80% capacity retention after 600 cycles.
基金support by the Department of Science&Technology of Zhejiang Province under grant No.2024C01095the Fundamental Research Funds for the Provincial Universities of Zhejiang under grant No.RF-C2022008the National Natural Science Foundation of China(NSFC)under grant Nos.U20A20253,52372235,and 22279116。
文摘Aqueous sodium-ion batteries(ASIBs)have garnered significant attention as promising candidates for large-scale energy storage applications.This interest is primarily due to their abundant resource availability,environmental friendliness,cost-effectiveness,and high safety.However,their electrochemical performance is limited by the thermodynamic properties of water molecules,resulting in inadequate cycling stability and insufficient specific energy density.To address these challenges,this study developed a hydrogen-bond enhanced urea-glycerol eutectic electrolyte(UGE)to expand the electrochemical stability window(ESW)of the electrolyte and suppress corresponding side reactions.The eutectic component disrupts the original hydrogen bonding network in water,creating a new,enhanced network that reduces the activity of free water and forms a uniform,dense passivation layer on the anode.As a result,the optimized composition of UGE exhibits a broad ESW of up to 3 V(-1.44 to 1.6 V vs.Ag/AgCl).The Prussian blue(PB)/UGE/NaTi_(2)(PO_(4))_(3)@C full cell exhibits an exceptionally long lifespan of 10,000 cycles at 10 C.This study introduces a low-cost,ultra-long-life ASIB system,utilizing a green and economical eutectic electrolyte,which expands the use of eutectic electrolytes in aqueous batteries and opens a new research horizon for constructing efficient electrochemical energy storage and conversion.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(No.2018R1A6A1A03025708).
文摘High-performance aqueous zinc(Zn)-ion batteries(AZIBs)have emerged as one of the greatest favorable candidates for next-generation energy storage systems because of their low cost,sustainability,high safety,and eco-friendliness.In this report,we prepared magnesium vanadate(MgVO)-based nanostructures by a facile single-step solvothermal method with varying experimental reaction times(1,3,and 6 h)and investigated the effect of the reaction time on the morphology and layered structure for MgVO-based compounds.The newly prepared MgVO-1 h,MgVO-3 h and MgVO-6 h samples were used as cathode materials for AZIBs.Compared to the MgVO-1 h and MgVO-6 h cathodes,the MgVO-3 h cathode showed a higher specific capacity of 492.74 mA h g^(-1) at 1 A g^(-1) over 500 cycles and excellent rate behavior(291.58 mA h g^(-1) at 3.75 A g^(-1))with high cycling stability(116%)over 2000 cycles at 5 A g^(-1).Moreover,the MgVO-3 h electrode exhibited good electrochemical performance owing to its fast Zn-ion diffusion kinetics.Additionally,various ex-situ analyses confirmed that the MgVO-3 h cathode displayed excellent insertion/extraction of Zn^(2+)ions during charge and discharge processes.This study offers an efficient method for the synthesis of nanostructured MgVO-based cathode materials for high-performance AZIBs.
基金Project supported by Publication Foundation of National Science and Technology Academic Books of China
文摘A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.
基金financially supported by the National Natural Science Foundation of China(Grant No.22075331,21905057)。
文摘Solid electrolyte interphase(SEI)is widely acknowledged as the most crucial and least comprehended component in secondary batteries.Particularly,fluorinated SEI derived from the decomposition of fluorinated salt/solvent electrolyte or additive has been widely applied to extend the lifespan of Li/Na anodes,and a similar strategy is being implemented for Zn metal electrodes.However,fluorine-containing electrolytes raise concerns regarding cost,toxicity,corrosivity,and environmental contamination.Moreover,the necessity and role of fluorine in the SEI component remain unclear,particularly in the aqueous system.Here,we report a fluorine-free inorganic-rich SEI layer in situ built by introducing a low-cost,low-concentration tetraethyl ammonium iodide(TEAI)into dilute aqueous ZnSO_(4)electrolyte.The TEAI additive is found to simultaneously modulate the Zn^(2+)solvation structure and optimize the chemisorption at the anode/electrolyte interface.The synergistic interaction between the I-/SO_(4)^(2-)anion-involved solvation structure and adsorbed TEA^(+)cations drives the formation of fluorine-free SEI with inorganics(Zn_(3)N_(2),Zn(IO_(3))_(2),Zn S,etc.),which are capable of providing fast Zn^(2+)transport ability,high-flux nucleation site,and preferential Zn(002)deposition.Besides the reductive decomposition with the formation of Irich SEI layer,the redox-active iodine species can rejuvenate inactive byproducts and dead Zn,allowing the interface self-healing and ensuring long-term interfacial stability.The TEAI-formulated electrolyte endows the Zn anode with excellent Zn reversibility by achieving dendrite-free Zn plating/stripping over 6500 h in the Zn||Zn symmetric battery at 1 mA cm^(-2).This study provides new insights into stabilizing Zn metal electrodes via robust fluorine-free interphases.
