A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal cry...A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.展开更多
(R)-2-hydroxy-3-phenylpropionic acid (PIP,) is an ideal antimicrobial compound with broad-spectrum activity against a wide range of Gram-positive bacteria, some Gram-negative bacteria, and fungi. We studied the bi...(R)-2-hydroxy-3-phenylpropionic acid (PIP,) is an ideal antimicrobial compound with broad-spectrum activity against a wide range of Gram-positive bacteria, some Gram-negative bacteria, and fungi. We studied the bioconversion of phenylpyruvate (PPA) to PLA using whole recombinant Escherichia coli cells in a series of buffer/organic solvent systems. Octane was found to be the best organic solvent. The optimum volume ratio of the water phase to the n-octane phase, conversion temperature, substrate concentration, and cell concentration were 6:4, 40 ℃, 12.5 g/L, and 30 g/L wet cells, respectively. Under the optimized conditions, the average PLA productivity in the aqueous/ n-octane system was 30.69% higher than that in the aqueous system, and 32.31 g/L PLA was obtained with the use of a stirred reactor (2-L scale). Taken together, our findings indicated that PLA biosynthesis was more efficient in an aqueous/n-octane biphasic system than in a monophasic aqueous system. The proposed biphasic system is an effective strategy for enhancing PLA yield and the biosynthesis of its analogues.展开更多
Based on the attributes of nonflammability,environmental benignity,and cost-effectiveness of aqueous electrolytes,as well as the favorable compatibility of zinc metal with them,aqueous zinc ions batteries(AZIBs)become...Based on the attributes of nonflammability,environmental benignity,and cost-effectiveness of aqueous electrolytes,as well as the favorable compatibility of zinc metal with them,aqueous zinc ions batteries(AZIBs)become the leading energy storage candidate to meet the requirements of safety and low cost.Yet,aqueous electrolytes,acting as a double-edged sword,also play a negative role by directly or indirectly causing various parasitic reactions at the zinc anode side.These reactions include hydrogen evolution reaction,passivation,and dendrites,resulting in poor Coulombic efficiency and short lifespan of AZIBs.A comprehensive review of aqueous electrolytes chemistry,zinc chemistry,mechanism and chemistry of parasitic reactions,and their relationship is lacking.Moreover,the understanding of strategies for suppressing parasitic reactions from an electrochemical perspective is not profound enough.In this review,firstly,the chemistry of electrolytes,zinc anodes,and parasitic reactions and their relationship in AZIBs are deeply disclosed.Subsequently,the strategies for suppressing parasitic reactions from the perspective of enhancing the inherent thermodynamic stability of electrolytes and anodes,and lowering the dynamics of parasitic reactions at Zn/electrolyte interfaces are reviewed.Lastly,the perspectives on the future development direction of aqueous electrolytes,zinc anodes,and Zn/electrolyte interfaces are presented.展开更多
Current lithium-ion batteries(LIBs)rely on organic liquid electrolytes that pose significant risks due to their flammability and toxicity.The potential for environmental pollution and explosions resulting from battery...Current lithium-ion batteries(LIBs)rely on organic liquid electrolytes that pose significant risks due to their flammability and toxicity.The potential for environmental pollution and explosions resulting from battery damage or fracture is a critical concern.Water-based(aqueous)electrolytes have been receiving attention as an alternative to organic electrolytes.However,a narrow electrochemicalstability window,water decomposition,and the consequent low battery operating voltage and energy density hinder the practical use of aqueous electrolytes.Therefore,developing novel aqueous electrolytes for sustainable,safe,high-performance LIBs remains challenging.This Review first commences by summarizing the roles and requirements of electrolytes–separators and then delineates the progression of aqueous electrolytes for LIBs,encompassing aqueous liquid and gel electrolyte development trends along with detailed principles of the electrolytes.These aqueous electrolytes are progressed based on strategies using superconcentrated salts,concentrated diluents,polymer additives,polymer networks,and artificial passivation layers,which are used for suppressing water decomposition and widening the electrochemical stability window of water of the electrolytes.In addition,this Review discusses potential strategies for the implementation of aqueous Li-metal batteries with improved electrolyte–electrode interfaces.A comprehensive understanding of each strategy in the aqueous system will assist in the design of an aqueous electrolyte and the development of sustainable and safe high-performance batteries.展开更多
Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the for...Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the formation of zinc dendrites and concurrent side reactions,which significantly diminish their overall service life,In this study,the glass fiber separator(GF) is modified using zeolite imidazole salt framework-8(ZIF-8),enabling the development of efficient AZIBs.ZIF-8,which is abundant in nitrogen content,efficiently regulates the desolvation of [Zn(H_(2)O)_(6)]^(2+) to inhibit hydrogen production.Moreover,it possesses abundant nanochannels that facilitate the uniform deposition of Zn~(2+) via a localized action,thereby hindering the formation of dendrites.The insulating properties of ZIF-8 help prevent Zn^(2+) and water from trapping electron reduction at the layer surface,which reduces corrosion of the zinc anode.Consequently,ZIF-8-GF achieves the even transport of Zn^(2+) and regulates the homogeneous deposition along the Zn(002) crystal surface,thus significantly enhancing the electrochemical performance of the AZIBs,In particular,the Zn|Zn symmetric cell with the ZIF-8-GF separator delivers a stable cycle life at0.5 mA cm^(-2) of 2300 h.The Zn|ZIF-8-GF|MnO_(2) cell exhibits reduced voltage polarization while maintaining a capacity retention rate(93.4%) after 1200 cycles at 1.2 A g^(-1) The unique design of the modified diaphragm provides a new approach to realizing high-performance AZIBs.展开更多
AIM:To investigate the efficacy of aflibercept combined with sub-tenon injection of triamcinolone acetonide(TA)in treating diabetic macular edema(DME)and to examine changes in growth factors and inflammatory mediator ...AIM:To investigate the efficacy of aflibercept combined with sub-tenon injection of triamcinolone acetonide(TA)in treating diabetic macular edema(DME)and to examine changes in growth factors and inflammatory mediator levels in aqueous humor after injection.METHODS:Totally 67 DME patients(67 eyes)and 30 cataract patients(32 eyes)were enrolled as the DME group and the control group,respectively.The DME group was divided into the aflibercept group(34 cases)and the aflibercept combined with TA group(combined group,33 cases).The aqueous humor of both groups was collected during the study period.The aqueous levels of vascular endothelial growth factor(VEGF),monocyte chemoattractant protein-1(MCP-1),interleukin-6(IL-6),interleukin-8(IL-8),and interleukin-1β(IL-1β)were detected using a microsphere suspension array technology(Luminex 200TM).Aqueous cytokines,best-corrected visual acuity(BCVA),central macular thickness(CMT),and complications before and after treatment were compared between the aflibercept group and combined group.RESULTS:The concentrations of VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor were significantly higher in the DME group than those of the control group(all P<0.01).After 1mo of surgery,the concentrations of VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor were significantly lower in the combined group than those of the aflibercept group(all P<0.01).The BCVA and CMT values of the two groups were statistically different after 1 and 2mo of treatment(P<0.01).However,the difference was not statistically significant after 3mo of treatment(P>0.05).CONCLUSION:The cytokines VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor of DME patients are significantly increased.Aflibercept and aflibercept combined with TA have good efficacy in DME patients,can effectively reduce CMT,improve the patient’s vision,and have high safety.Aflibercept combined with TA can quickly downregulate the aqueous humor cytokines and help to relieve macular edema rapidly.However,the long-term efficacy is comparable to that of aflibercept alone.展开更多
With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diame...With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.展开更多
Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,hi...Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.展开更多
Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organi...Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organic-hybridized electrolyte designs,however,at the expense of cost and safety.Here,we report the prolonged cycling of ASIBs in routine dilute electrolytes by employing artificial electrode coatings consisting of NaX zeolite and NaOH-neutralized perfluorinated sulfonic polymer.The as-formed composite interphase exhibits a molecularsieving effect jointly played by zeolite channels and size-shrunken ionic domains in the polymer matrix,which enables high rejection of hydrated Na^(+)ions while allowing fast dehydrated Na^(+)permeance.Applying this coating to electrode surfaces expands the electrochemical window of a practically feasible 2 mol kg^(-1) sodium trifluoromethanesulfonate aqueous electrolyte to 2.70 V and affords Na_(2)MnFe(CN)_(6)//NaTi_(2)(PO_(4))_(3) full cells with an unprecedented cycling stability of 94.9%capacity retention after 200 cycles at 1 C.Combined with emerging electrolyte modifications,this molecular-sieving interphase brings amplified benefits in long-term operation of ASIBs.展开更多
Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonethel...Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.展开更多
Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,s...Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,safety and low cost.However,the underexplored redox properties of organic materials and the narrow thermodynamic electrolysis window of water(1.23 V)hinder their wide applications.Therefore,seeking suitable organic redox couples and aqueous electrolytes with a high output voltage is highly suggested for advancing the aqueous organic RFBs.In this work,the functionalized phenazine and nitroxyl radical with electron-donating and electron-withdrawing group exhibit redox potential of-0.88 V and 0.78 V vs.Ag,respectively,in“water-in-ionic liquid”supporting electrolytes.Raman spectra reveal that the activity of water is largely suppressed in“water-in-ionic liquid”due to the enhanced hydrogen bond interactions between ionic liquid and water,enabling an electrochemical stability window above 3 V.“Water-in-ionic liquid”supporting electrolytes help to shift redox potential of nitroxyl radical and enable the redox activity of functionalized phenazine.The assembled aqueous RFB allows a theoretical cell voltage of 1.66 V and shows a practical discharge voltage of 1.5 V in the“water-in-ionic liquid”electrolytes.Meanwhile,capacity retention of 99.91%per cycle is achieved over 500 charge/discharge cycles.A power density of 112 mW cm^(-2) is obtained at a current density of 30 mA cm^(-2).This work highlights the importance of rationally combining supporting electrolytes and organic molecules to achieve high-voltage aqueous RFBs.展开更多
Aqueous zinc-ion battery systems are attractive for next-generation energy storage devices,however,the unstable electrode electrolyte interphase,especially cathode electrolyte interphase(CEI),has induced rapid capacit...Aqueous zinc-ion battery systems are attractive for next-generation energy storage devices,however,the unstable electrode electrolyte interphase,especially cathode electrolyte interphase(CEI),has induced rapid capacity attenuation,insufficient cycle life,and severe safety issues.Evolving the researching of CEI formation,composition,dynamic structure,and reaction mechanisms would help in understanding the fundamental electrochemistry at CEI such as electron and ion transport processes,further strengthening the specific capacity,rate,and cycle performance of the cathode materials.In this review,we summarized the latest progress in understanding interfacial reaction mechanisms and ion dynamic behavior,emphasizing the impact of surface-specific adsorption and solvation behaviors on the interface's ultimate structure and chemical composition.Subsequently,the significant challenges that persist in CEI formation mechanisms,such as cathodic dissolution,by-product formation,electrostatic interactions,constrained electrochemical windows,oxygen evolution reaction,overpotentials,phase transitions,and additional factors,were discussed.These challenges are explored to identify triggers contributing to the depletion of active materials and alterations in the composition or state of the CEI.Ultimately,with a deep comprehension of interfacial behaviors,the review articulates innovative optimization strategies through a detailed categorization of approaches in electrolyte engineering,cathode engineering,and artificial CEI development.Furthermore,future challenges and development directions of CEI are presented.We hope to offer insights for constructing robust CEI films to achieve high performance aqueous zinc-ion batteries.展开更多
Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storag...Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storage technology for the grid-scale integration of renewable electricity.pH-neutral AORFBs that feature high safety,low corrosivity,and environmental benignity are particularly promising,and their battery performance is significantly impacted by redox-active molecules and ion-exchange membranes(IEMs).Here,representative anolytes and catholytes engineered for use in pH-neutral AORFBs are outlined and summarized,as well as their side reactions that cause irreversible battery capacity fading.In addition,the recent achievements of IEMs for pH-neutral AORFBs are discussed,with a focus on the construction and tuning of ion transport channels.Finally,the critical challenges and potential research opportunities for developing practically relevant pH-neutral AORFBs are presented.展开更多
Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be...Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be solved for extended storage and cycle life.Here,we proposed that an electrolyte additive with an intermediate chelation strength of zinc ion—strong enough to exclude water molecules from the zinc metal-electrolyte interface and not too strong to cause a significant energy barrier for zinc ion dissociation—can benefit the electrochemical stability by suppressing hydrogen evolution reaction,overpotential growth,and den-drite formation.Penta-sodium diethylene-triaminepentaacetic acid salt was selected for such a purpose.It has a suitable chelating ability in aqueous solutions to adjust solvation sheath and can be readily polarized under electrical loading conditions to further improve the passivation.Zn||Zn symmetric cells can be stably operated over 3500 h at 1 mA cm^(-2).Zn||NH4V4O10 full cells with the additive show great cycling stability with 84.6%capacity retention after 500 cycles at 1 A g^(-1).Since the additive not only reduces H2 evolution and corrosion but also modifies Zn2+diffusion and deposition,highlyreversible Zn electrodes can be achieved as verified by the experimental results.Our work offers a practical approach to the logical design of reliable electrolytes for high-performance aqueous batteries.展开更多
With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy stor...With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.展开更多
As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g...As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g^(-1))of multivalent Zn2+ion.However,the growth of Zn dendrites and the formation of irreversible surface reaction byproducts pose challenges for ensuring a long battery lifespan and commercialization.Herein,the Cu foil coated with a single-walled carbon nanotube(SWCNT)layer using a facile doctor blade casting method is utilized.The SWCNT-coated Cu foil demonstrates a significantly longer battery lifespan compared to the bare Cu in the half-cell tests.Through operando optical microscopy imaging,we are able to provide intuitive evidence that Zn deposition occurs between the carbon nanotube(CNT)coating and Cu substrate,in agreement with the computational results.Also,with various imaging techniques,the flat morphology and homogeneous distribution of Zn beneath the SWCNT layer are demonstrated.In addition,the full-cell using CNT-coated Cu exhibits a long cycle life compared to the control group,thereby demonstrating improved electrochemical performance with limited Zn for the cycling process.展开更多
The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from struc...The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.展开更多
The voltage drop appearing at Mg anode-electrolyte interface is a critical issue for the battery power and energy density of aqueous primary Mg-air batteries.The respective voltage loss is typically assigned to the de...The voltage drop appearing at Mg anode-electrolyte interface is a critical issue for the battery power and energy density of aqueous primary Mg-air batteries.The respective voltage loss is typically assigned to the deposits layer forming on the anode surface during discharge.In this work,we experimentally and computationally investigate the critical factors affecting the voltage drop at Mg anode towards a deeper understanding of the contribution of deposit and its growth.A two-dimensional(2D)mathematical model is proposed to compute the voltage drop of Mg-0.15Ca wt.%alloy(Mg-0.15Ca)by means of a semi-empirical formulas and experiments-based modification model,considering the effect of discharge current density,the negative difference effect(NDE)and surface deposits layer itself.This model is utilized to simulate the discharge potential of the anode at predefined experimental current densities.The computed voltage drop(half-cell voltage)is in good agreement with the experimental value.The applicability of the mathematical model is successfully validated on the second material(namely high-purity Mg).展开更多
Aqueous electrochromic battery(ECB)has shown intense potential for achieving energy storage and saving simultaneously.While tungsten oxide(WO_(3))is the most promising EC material for commercialization,the cycling sta...Aqueous electrochromic battery(ECB)has shown intense potential for achieving energy storage and saving simultaneously.While tungsten oxide(WO_(3))is the most promising EC material for commercialization,the cycling stability of WO_(3)-based aqueous ECBs is currently unsatisfactory due to the repeated phase transition during the redox process and the corrosion by acidic electrolytes.Herein,we present a titanium-tungsten oxide alloy(Ti-WO_(3))with controllable morphology and crystal phase synthesized by a facile hot injection method to overcome the challenges.In contrast to conventional monoclinic WO_(3),the Ti-WO_(3)nanorods can stably maintain their cubic crystal phase during the redox reaction in an acidic electrolyte,thus leading to dramatically enhanced response speed and cycling stability,Specifically,when working in a well-matched hybrid Al^(3+)/Zn^(2+)aqueous electrolyte,our phasetransition-free cubic Ti-WO_(3)exhibits an ultra-high cycling stability(>20000 cycles),fast response speed(3,95 s/4,65 s for bleaching/coloring),as well as excellent discharge areal capacity of 214.5 mA h m^(-2),We further fabricate a fully complementa ry aqueous electrochromic device,for the first time,using a Ti-WO_(3)/Prussian blue device architecture.Remarkably,the complementary ECB shows>10000 stable operation cycles,attesting to the feasibility of our Ti-WO_(3)for practical applications.Our work validates the significance of inhibiting the phase transitions of WO_(3)during the electrochromic process for realizing highly cyclable aqueous ECB,which can possibly provide a generalized design guidance for other high-quality metallic oxides for electrochemical applications.展开更多
Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are stil...Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.展开更多
基金the financial supports from the National Natural Science Foundation of China(22322803,22178059,22208054,22221005,22072019)Key Technologies Innovation and Industrialization Projects of Fujian Province(2022G031)Qingyuan Innovation Laboratory(00121002,00523005)。
文摘A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.
基金Project supported by the National Natural Science Foundation of China(Nos.31470092 and 31501459)the Natural Science Youth Foundation of Jiangsu Province(No.BK20130380)China
文摘(R)-2-hydroxy-3-phenylpropionic acid (PIP,) is an ideal antimicrobial compound with broad-spectrum activity against a wide range of Gram-positive bacteria, some Gram-negative bacteria, and fungi. We studied the bioconversion of phenylpyruvate (PPA) to PLA using whole recombinant Escherichia coli cells in a series of buffer/organic solvent systems. Octane was found to be the best organic solvent. The optimum volume ratio of the water phase to the n-octane phase, conversion temperature, substrate concentration, and cell concentration were 6:4, 40 ℃, 12.5 g/L, and 30 g/L wet cells, respectively. Under the optimized conditions, the average PLA productivity in the aqueous/ n-octane system was 30.69% higher than that in the aqueous system, and 32.31 g/L PLA was obtained with the use of a stirred reactor (2-L scale). Taken together, our findings indicated that PLA biosynthesis was more efficient in an aqueous/n-octane biphasic system than in a monophasic aqueous system. The proposed biphasic system is an effective strategy for enhancing PLA yield and the biosynthesis of its analogues.
基金supported by the Academic Excellence Foundation of BUAA for PhD Studentsthe National Natural Science Foundation of China (Grant Number: 52001016)
文摘Based on the attributes of nonflammability,environmental benignity,and cost-effectiveness of aqueous electrolytes,as well as the favorable compatibility of zinc metal with them,aqueous zinc ions batteries(AZIBs)become the leading energy storage candidate to meet the requirements of safety and low cost.Yet,aqueous electrolytes,acting as a double-edged sword,also play a negative role by directly or indirectly causing various parasitic reactions at the zinc anode side.These reactions include hydrogen evolution reaction,passivation,and dendrites,resulting in poor Coulombic efficiency and short lifespan of AZIBs.A comprehensive review of aqueous electrolytes chemistry,zinc chemistry,mechanism and chemistry of parasitic reactions,and their relationship is lacking.Moreover,the understanding of strategies for suppressing parasitic reactions from an electrochemical perspective is not profound enough.In this review,firstly,the chemistry of electrolytes,zinc anodes,and parasitic reactions and their relationship in AZIBs are deeply disclosed.Subsequently,the strategies for suppressing parasitic reactions from the perspective of enhancing the inherent thermodynamic stability of electrolytes and anodes,and lowering the dynamics of parasitic reactions at Zn/electrolyte interfaces are reviewed.Lastly,the perspectives on the future development direction of aqueous electrolytes,zinc anodes,and Zn/electrolyte interfaces are presented.
基金the National Research Foundation(NRF)of Korea(No.2022R1A2B5B02002097),funded by the Korea government(MSIT).
文摘Current lithium-ion batteries(LIBs)rely on organic liquid electrolytes that pose significant risks due to their flammability and toxicity.The potential for environmental pollution and explosions resulting from battery damage or fracture is a critical concern.Water-based(aqueous)electrolytes have been receiving attention as an alternative to organic electrolytes.However,a narrow electrochemicalstability window,water decomposition,and the consequent low battery operating voltage and energy density hinder the practical use of aqueous electrolytes.Therefore,developing novel aqueous electrolytes for sustainable,safe,high-performance LIBs remains challenging.This Review first commences by summarizing the roles and requirements of electrolytes–separators and then delineates the progression of aqueous electrolytes for LIBs,encompassing aqueous liquid and gel electrolyte development trends along with detailed principles of the electrolytes.These aqueous electrolytes are progressed based on strategies using superconcentrated salts,concentrated diluents,polymer additives,polymer networks,and artificial passivation layers,which are used for suppressing water decomposition and widening the electrochemical stability window of water of the electrolytes.In addition,this Review discusses potential strategies for the implementation of aqueous Li-metal batteries with improved electrolyte–electrode interfaces.A comprehensive understanding of each strategy in the aqueous system will assist in the design of an aqueous electrolyte and the development of sustainable and safe high-performance batteries.
基金financially supported by National Natural Science Foundation of China(No.51872090,51772097)Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433)+2 种基金Youth Talent Program of Hebei Provincial Education Department(No.BJ2018020)Natural Science Foundation of Hebei Province(No.E2020209151)the financial support from Donghua University(101-08-0241022,23D210105,and 101-07-005759)。
文摘Aqueous zinc-ion batteries(AZIBs) hold great promise as a viable alternative to lithium-ion batteries owing to their high energy density and environmental friendliness.However,AZIBs are consistently plagued by the formation of zinc dendrites and concurrent side reactions,which significantly diminish their overall service life,In this study,the glass fiber separator(GF) is modified using zeolite imidazole salt framework-8(ZIF-8),enabling the development of efficient AZIBs.ZIF-8,which is abundant in nitrogen content,efficiently regulates the desolvation of [Zn(H_(2)O)_(6)]^(2+) to inhibit hydrogen production.Moreover,it possesses abundant nanochannels that facilitate the uniform deposition of Zn~(2+) via a localized action,thereby hindering the formation of dendrites.The insulating properties of ZIF-8 help prevent Zn^(2+) and water from trapping electron reduction at the layer surface,which reduces corrosion of the zinc anode.Consequently,ZIF-8-GF achieves the even transport of Zn^(2+) and regulates the homogeneous deposition along the Zn(002) crystal surface,thus significantly enhancing the electrochemical performance of the AZIBs,In particular,the Zn|Zn symmetric cell with the ZIF-8-GF separator delivers a stable cycle life at0.5 mA cm^(-2) of 2300 h.The Zn|ZIF-8-GF|MnO_(2) cell exhibits reduced voltage polarization while maintaining a capacity retention rate(93.4%) after 1200 cycles at 1.2 A g^(-1) The unique design of the modified diaphragm provides a new approach to realizing high-performance AZIBs.
基金Supported by the Shenzhen Science and Technology Innovation Committee,China(No.JCYJ20220530164600002)Scientific Research Program of Xiangjiang Philanthropy FoundationScience Research Grant of Aier Eye Hospital Group(No.AF2201D06).
文摘AIM:To investigate the efficacy of aflibercept combined with sub-tenon injection of triamcinolone acetonide(TA)in treating diabetic macular edema(DME)and to examine changes in growth factors and inflammatory mediator levels in aqueous humor after injection.METHODS:Totally 67 DME patients(67 eyes)and 30 cataract patients(32 eyes)were enrolled as the DME group and the control group,respectively.The DME group was divided into the aflibercept group(34 cases)and the aflibercept combined with TA group(combined group,33 cases).The aqueous humor of both groups was collected during the study period.The aqueous levels of vascular endothelial growth factor(VEGF),monocyte chemoattractant protein-1(MCP-1),interleukin-6(IL-6),interleukin-8(IL-8),and interleukin-1β(IL-1β)were detected using a microsphere suspension array technology(Luminex 200TM).Aqueous cytokines,best-corrected visual acuity(BCVA),central macular thickness(CMT),and complications before and after treatment were compared between the aflibercept group and combined group.RESULTS:The concentrations of VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor were significantly higher in the DME group than those of the control group(all P<0.01).After 1mo of surgery,the concentrations of VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor were significantly lower in the combined group than those of the aflibercept group(all P<0.01).The BCVA and CMT values of the two groups were statistically different after 1 and 2mo of treatment(P<0.01).However,the difference was not statistically significant after 3mo of treatment(P>0.05).CONCLUSION:The cytokines VEGF,MCP-1,IL-6,and IL-8 in the aqueous humor of DME patients are significantly increased.Aflibercept and aflibercept combined with TA have good efficacy in DME patients,can effectively reduce CMT,improve the patient’s vision,and have high safety.Aflibercept combined with TA can quickly downregulate the aqueous humor cytokines and help to relieve macular edema rapidly.However,the long-term efficacy is comparable to that of aflibercept alone.
基金National Natural Science Foundation of China(52202299)the Analytical&Testing Center of Northwestern Polytechnical University(2022T006).
文摘With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.
基金the financial support from the Australian Research Council,Centre for Materials Science,Queensland University of Technologythe Supported by the Fundamental Research Funds for the Central Universities。
文摘Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.
基金supported by the National Key R&D Program of China(Grant No.2022YFB2402604)the National Natural Science Foundation of China(21975271,22209194)+3 种基金Shandong Natural Science Foundation(ZR2020ZD07,ZR2023YQ010 and ZR2021QB106)the Taishan Scholars of Shandong Province(No.ts201511063,tsqn202211277)the Shandong Energy Institute(SEI I202127)Qingdao New Energy Shandong Laboratory(QIBEBT/SEI/QNESLS202304).
文摘Aqueous sodium-ion batteries are known for poor rechargeability because of the competitive water decomposition reactions and the high electrode solubility.Improvements have been reported by saltconcentrated and organic-hybridized electrolyte designs,however,at the expense of cost and safety.Here,we report the prolonged cycling of ASIBs in routine dilute electrolytes by employing artificial electrode coatings consisting of NaX zeolite and NaOH-neutralized perfluorinated sulfonic polymer.The as-formed composite interphase exhibits a molecularsieving effect jointly played by zeolite channels and size-shrunken ionic domains in the polymer matrix,which enables high rejection of hydrated Na^(+)ions while allowing fast dehydrated Na^(+)permeance.Applying this coating to electrode surfaces expands the electrochemical window of a practically feasible 2 mol kg^(-1) sodium trifluoromethanesulfonate aqueous electrolyte to 2.70 V and affords Na_(2)MnFe(CN)_(6)//NaTi_(2)(PO_(4))_(3) full cells with an unprecedented cycling stability of 94.9%capacity retention after 200 cycles at 1 C.Combined with emerging electrolyte modifications,this molecular-sieving interphase brings amplified benefits in long-term operation of ASIBs.
基金This work was supported by the National Natural Science Foundation of China(52373306,52172233,and 51832004)the Natural Science Foundation of Hubei Province(2023AFA053)the Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(2021CXLH0007).
文摘Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.
基金support from China Postdoctoral Science Foundation(Grant No.2021M690960)China CSC abroad studying fellowship.R.C.thanks the KIST Europe basic research funding“new electrolytes for redox flow batteries”and the partial financial support from the CMBlu Energy AG.Y.Z.thanks to the support received from the National Natural Science Foundation of China(Grant No.22002009)the Natural Science Foundation of Hunan Province(Grant No.2021JJ40565).
文摘Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,safety and low cost.However,the underexplored redox properties of organic materials and the narrow thermodynamic electrolysis window of water(1.23 V)hinder their wide applications.Therefore,seeking suitable organic redox couples and aqueous electrolytes with a high output voltage is highly suggested for advancing the aqueous organic RFBs.In this work,the functionalized phenazine and nitroxyl radical with electron-donating and electron-withdrawing group exhibit redox potential of-0.88 V and 0.78 V vs.Ag,respectively,in“water-in-ionic liquid”supporting electrolytes.Raman spectra reveal that the activity of water is largely suppressed in“water-in-ionic liquid”due to the enhanced hydrogen bond interactions between ionic liquid and water,enabling an electrochemical stability window above 3 V.“Water-in-ionic liquid”supporting electrolytes help to shift redox potential of nitroxyl radical and enable the redox activity of functionalized phenazine.The assembled aqueous RFB allows a theoretical cell voltage of 1.66 V and shows a practical discharge voltage of 1.5 V in the“water-in-ionic liquid”electrolytes.Meanwhile,capacity retention of 99.91%per cycle is achieved over 500 charge/discharge cycles.A power density of 112 mW cm^(-2) is obtained at a current density of 30 mA cm^(-2).This work highlights the importance of rationally combining supporting electrolytes and organic molecules to achieve high-voltage aqueous RFBs.
基金supported by the Fundamental Research Funds for the Central Universities,Natural Science Foundation of China(Nos.52202100 and U2004209)China Postdoctoral Science Foundation(No.314500)Postgraduate Research&Practice Innovation Program of Jiangsu Province(Nos.KYCX23_0451).
文摘Aqueous zinc-ion battery systems are attractive for next-generation energy storage devices,however,the unstable electrode electrolyte interphase,especially cathode electrolyte interphase(CEI),has induced rapid capacity attenuation,insufficient cycle life,and severe safety issues.Evolving the researching of CEI formation,composition,dynamic structure,and reaction mechanisms would help in understanding the fundamental electrochemistry at CEI such as electron and ion transport processes,further strengthening the specific capacity,rate,and cycle performance of the cathode materials.In this review,we summarized the latest progress in understanding interfacial reaction mechanisms and ion dynamic behavior,emphasizing the impact of surface-specific adsorption and solvation behaviors on the interface's ultimate structure and chemical composition.Subsequently,the significant challenges that persist in CEI formation mechanisms,such as cathodic dissolution,by-product formation,electrostatic interactions,constrained electrochemical windows,oxygen evolution reaction,overpotentials,phase transitions,and additional factors,were discussed.These challenges are explored to identify triggers contributing to the depletion of active materials and alterations in the composition or state of the CEI.Ultimately,with a deep comprehension of interfacial behaviors,the review articulates innovative optimization strategies through a detailed categorization of approaches in electrolyte engineering,cathode engineering,and artificial CEI development.Furthermore,future challenges and development directions of CEI are presented.We hope to offer insights for constructing robust CEI films to achieve high performance aqueous zinc-ion batteries.
基金funded by the National Key Research and Development Program of China(Nos.2022YFB3805303,2022YFB3805304)the National Natural Science Foundation of China(Grant/Award Numbers:22308345,U20A20127)+1 种基金the Anhui Provincial Natural Science Foundation(No.2308085QB68)the Fundamental Research Funds for the Central Universities(No.WK2060000059).
文摘Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storage technology for the grid-scale integration of renewable electricity.pH-neutral AORFBs that feature high safety,low corrosivity,and environmental benignity are particularly promising,and their battery performance is significantly impacted by redox-active molecules and ion-exchange membranes(IEMs).Here,representative anolytes and catholytes engineered for use in pH-neutral AORFBs are outlined and summarized,as well as their side reactions that cause irreversible battery capacity fading.In addition,the recent achievements of IEMs for pH-neutral AORFBs are discussed,with a focus on the construction and tuning of ion transport channels.Finally,the critical challenges and potential research opportunities for developing practically relevant pH-neutral AORFBs are presented.
基金This work is financially supported by National Natural Science Foundation of China(NSFC-No.52173257 and 52372064).
文摘Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be solved for extended storage and cycle life.Here,we proposed that an electrolyte additive with an intermediate chelation strength of zinc ion—strong enough to exclude water molecules from the zinc metal-electrolyte interface and not too strong to cause a significant energy barrier for zinc ion dissociation—can benefit the electrochemical stability by suppressing hydrogen evolution reaction,overpotential growth,and den-drite formation.Penta-sodium diethylene-triaminepentaacetic acid salt was selected for such a purpose.It has a suitable chelating ability in aqueous solutions to adjust solvation sheath and can be readily polarized under electrical loading conditions to further improve the passivation.Zn||Zn symmetric cells can be stably operated over 3500 h at 1 mA cm^(-2).Zn||NH4V4O10 full cells with the additive show great cycling stability with 84.6%capacity retention after 500 cycles at 1 A g^(-1).Since the additive not only reduces H2 evolution and corrosion but also modifies Zn2+diffusion and deposition,highlyreversible Zn electrodes can be achieved as verified by the experimental results.Our work offers a practical approach to the logical design of reliable electrolytes for high-performance aqueous batteries.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097,22304055)the Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+4 种基金the Youth Talent Program of Hebei Provincial Education Department(BJ2018020)the Natural Science Foundation of Hebei Province(E2020209151,E2022209158,B2022209026,D2023209012)the Central Guiding Local Science and Technology Development Fund Project(236Z4409G)the Science and Technology Project of Hebei Education Department(SLRC2019028)the Science and Technology Planning Project of Tangshan City(22130227H)。
文摘With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.
基金Ministry of Science and ICT,South Korea,Grant/Award Number:C310200National Research Foundation of Korea(NRF),Grant/Award Number:2020R1C1C1012308。
文摘As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g^(-1))of multivalent Zn2+ion.However,the growth of Zn dendrites and the formation of irreversible surface reaction byproducts pose challenges for ensuring a long battery lifespan and commercialization.Herein,the Cu foil coated with a single-walled carbon nanotube(SWCNT)layer using a facile doctor blade casting method is utilized.The SWCNT-coated Cu foil demonstrates a significantly longer battery lifespan compared to the bare Cu in the half-cell tests.Through operando optical microscopy imaging,we are able to provide intuitive evidence that Zn deposition occurs between the carbon nanotube(CNT)coating and Cu substrate,in agreement with the computational results.Also,with various imaging techniques,the flat morphology and homogeneous distribution of Zn beneath the SWCNT layer are demonstrated.In addition,the full-cell using CNT-coated Cu exhibits a long cycle life compared to the control group,thereby demonstrating improved electrochemical performance with limited Zn for the cycling process.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korean Government(NRF-2021R1A4A1030318,NRF-2022R1C1C1011386,NRF-2020M3H4A1A03084258)supported by the"Regional Innovation Strategy(RIS)"through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(2021RIS-003)
文摘The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.
基金the China Scholarship Council for the award of fellowship and funding No.201908510177 and No.202106050030funded by dtec.bw-Digitalization and Technology Research Center of the Bundeswehr which project DMF+1 种基金The AMABML project founded by the Zentrum für Hochleistungsmaterialien(ZHM)DEZAIN project for financial support via grant from GIF,the German-Israeli Foundation for Scientific Research and Development。
文摘The voltage drop appearing at Mg anode-electrolyte interface is a critical issue for the battery power and energy density of aqueous primary Mg-air batteries.The respective voltage loss is typically assigned to the deposits layer forming on the anode surface during discharge.In this work,we experimentally and computationally investigate the critical factors affecting the voltage drop at Mg anode towards a deeper understanding of the contribution of deposit and its growth.A two-dimensional(2D)mathematical model is proposed to compute the voltage drop of Mg-0.15Ca wt.%alloy(Mg-0.15Ca)by means of a semi-empirical formulas and experiments-based modification model,considering the effect of discharge current density,the negative difference effect(NDE)and surface deposits layer itself.This model is utilized to simulate the discharge potential of the anode at predefined experimental current densities.The computed voltage drop(half-cell voltage)is in good agreement with the experimental value.The applicability of the mathematical model is successfully validated on the second material(namely high-purity Mg).
基金funded by the Science and Technology Development Fund,Macao SAR(File no.0052/2021/AGJ,0027/2023/AMJ,0083/2023/ITP2 and 0107/2023/AFJ)the Multi-Year Research Grants(MYRG2022-00063-IAPME,MYRG-GRG2023-00230-IAPME-UMDF)from the University of Macao+1 种基金the Guangdong Science and Technology Plan(2022A0505020022)the Major Science and Technology Research and Development Project of Jiangxi Province(20223AAE01003)。
文摘Aqueous electrochromic battery(ECB)has shown intense potential for achieving energy storage and saving simultaneously.While tungsten oxide(WO_(3))is the most promising EC material for commercialization,the cycling stability of WO_(3)-based aqueous ECBs is currently unsatisfactory due to the repeated phase transition during the redox process and the corrosion by acidic electrolytes.Herein,we present a titanium-tungsten oxide alloy(Ti-WO_(3))with controllable morphology and crystal phase synthesized by a facile hot injection method to overcome the challenges.In contrast to conventional monoclinic WO_(3),the Ti-WO_(3)nanorods can stably maintain their cubic crystal phase during the redox reaction in an acidic electrolyte,thus leading to dramatically enhanced response speed and cycling stability,Specifically,when working in a well-matched hybrid Al^(3+)/Zn^(2+)aqueous electrolyte,our phasetransition-free cubic Ti-WO_(3)exhibits an ultra-high cycling stability(>20000 cycles),fast response speed(3,95 s/4,65 s for bleaching/coloring),as well as excellent discharge areal capacity of 214.5 mA h m^(-2),We further fabricate a fully complementa ry aqueous electrochromic device,for the first time,using a Ti-WO_(3)/Prussian blue device architecture.Remarkably,the complementary ECB shows>10000 stable operation cycles,attesting to the feasibility of our Ti-WO_(3)for practical applications.Our work validates the significance of inhibiting the phase transitions of WO_(3)during the electrochromic process for realizing highly cyclable aqueous ECB,which can possibly provide a generalized design guidance for other high-quality metallic oxides for electrochemical applications.
基金financially supported by the National Natural Science Foundation of China(U21A2077)the Taishan Scholar Project Foundation of Shandong Province(ts20190908)the Natural Science Foundation of Shandong Province(ZR2022MB084 and ZR2021ZD05).
文摘Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.