A novel improvement strategy and a comprehensive mechanism insight for α-MnO_(2) energy storage in rechargeable aqueous zinc-ion batteries

Aqueous zinc-ion batteries have been regarded as the most potential candidate to substitute lithium-ion batteries.However,many serious challenges such as suppressing zinc dendrite growth and undesirable reactions,and achieving fully accepted mechanism also have not been solved.Herein,the commensal composite microspheres withα-MnO_(2) nano-wires and carbon nanotubes were achieved and could effectively suppress ZnSO_(4)·3Zn(OH)_(2)·nH_(2)O rampant crystallization.The electrode assembled with the microspheres delivered a high initial capacity at a current density of 0.05 A g^(-1) and maintained a significantly prominent capacity retention of 88%over 2500 cycles.Furthermore,a novel energy-storage mechanism,in which multivalent manganese oxides play a synergistic effect,was comprehen-sively investigated by the quantitative and qualitative analysis for ZnSO_(4)·3Zn(OH)_(2)·nH_(2)O.The capacity contribution of multivalent manganese oxides and the crystal structure dissection in the transformed processes were completely identified.Therefore,our research could provide a novel strategy for designing improved electrode structure and a comprehensive understanding of the energy storage mechanism of α-MnO_(2) cathodes.

Understanding of the charge storage mechanism of MnO_(2)-based aqueous zinc-ion batteries:Reaction processes and regulation strategies

Though secondary aqueous Zn ion batteries(AZIBs)have been received broad concern in recent years,the development of suitable cathode materials of AZIBs is still a big challenge.The MnO_(2) has been deemed as one of most hopeful cathode materials of AZIBs on account of some extraordinary merits,such as richly natural resources,low toxicity,high discharge potential,and large theoretical capacity.However,the crystal structure diversity of MnO_(2) results in an obvious various of charge storage mechanisms,which can cause great differences in electrochemical performance.Furthermore,several challenges,including intrinsic poor conductivity,dissolution of manganese and sluggish ion transport dynamics should be conquered before real practice.This work focuses on the reaction mechanisms and recent progress of MnO_(2)-based materials of AZIBs.In this review,a detailed review of the reaction mechanisms and optimal ways for enhancing electrochemical performance for MnO_(2)-based materials is proposed.At last,a number of viewpoints on challenges,future development direction,and foreground of MnO_(2)-based materials of aqueous zinc ions batteries are put forward.This review clarifies reaction mechanism of MnO_(2)-based materials of AZIBs,and offers a new perspective for the future invention in MnO_(2)-based cathode materials,thus accelerate the extensive development and commercialization practice of aqueous zinc ions batteries.

ZnO-Embedded Expanded Graphite Composite Anodes with Controlled Charge Storage Mechanism Enabling Operation of Lithium-Ion Batteries at Ultra-Low Temperatures

As lithium(Li)-ion batteries expand their applications,operating over a wide temperature range becomes increasingly important.However,the lowtemperature performance of conventional graphite anodes is severely hampered by the poor diffusion kinetics of Li ions(Li^(+)).Here,zinc oxide(ZnO) nanoparticles are incorporated into the expanded graphite to improve Li^(+)diffusion kinetics,resulting in a significant improvement in lowtemperature performance.The ZnO-embedded expanded graphite anodes are investigated with different amounts of ZnO to establish the structurecharge storage mechanism-performance relationship with a focus on lowtemperature applications.Electrochemical analysis reveals that the ZnOembedded expanded graphite anode with nano-sized ZnO maintains a large portion of the diffusion-controlled charge storage mechanism at an ultra-low temperature of-50℃ Due to this significantly enhanced Li^(+)diffusion rate,a full cell with the ZnO-embedded expanded graphite anode and a LiNi_(0.88)Co_(0.09)Al_(0.03)O_(2)cathode delivers high capacities of 176 mAh g^(-1)at20℃ and 86 mAh g^(-1)at-50℃ at a high rate of 1 C.The outstanding low-temperature performance of the composite anode by improving the Li^(+)diffusion kinetics provides important scientific insights into the fundamental design principles of anodes for low-temperature Li-ion battery operation.

Methylene blue intercalated vanadium oxide with synergistic energy storage mechanism for highly efficient aqueous zinc ion batteries

With the rise of aqueous multivalent rechargeable batteries,inorganic-organic hybrid cathodes have attracted more and more attention due to the complement of each other’s advantages.Herein,a strategy of designing hybrid cathode is adopted for high efficient aqueous zinc-ion batteries(AZIBs).Methylene blue(MB)intercalated vanadium oxide(HVO-MB)was synthesized through sol-gel and ion exchange method.Compared with other organic-inorganic intercalation cathode,not only can the MB intercalation enlarge the HVO interlayer spacing to improve ion mobility,but also provide coordination reactions with the Zn^(2+)to enhance the intrinsic electrochemical reaction kinetics of the hybrid electrode.As a key component for the cathode of AZIBs,HVO-MB contributes a specific capacity of 418 mA h g^(-1) at 0.1 A g^(-1),high rate capability(243 mA h g^(-1) at 5 A g^(-1))and extraordinary stability(88%of capacity retention after 2000cycles at a high current density of 5 A g^(-1))in 3 M Zn(CF_(3)SO_(3))_(2) aqueous electrolyte.The electrochemical kinetics reveals HVO-MB characterized with large pseudocapacitance charge storage behavior due to the fast ion migration provided by the coordination reaction and expanded interlayer distance.Furthermore,a mixed energy storage mechanism involving Zn^(2+)insertion and coordination reaction is confirmed by various ex-situ characterization.Thus,this work opens up a new path for constructing the high performance cathode of AZIBs through organic-inorganic hybridization.

High-Resolution Mass Spectroscopy for Revealing the Charge Storage Mechanism in Batteries: Oxamide Materials as an Example

The pursuit of high-performance electrode materials is highly desired to meet the demand of batteries with high energy and power density.However,a deep understanding of the charge storage mechanism is always challenging,which limits the development of advanced electrode materials.Herein,high-resolution mass spectroscopy(HR-MS)is employed to detect the evolution of organic electrode materials during the redox process and reveal the charge storage mechanism,by using small molecular oxamides as an example,which have ortho-carbonyls and are therefore potential electrochemical active materials for batteries.The HR-MS results adequately proved that the oxamides could reversibly store lithium ions in the voltage window of 1.5–3.8 V.Upon deeper reduction,the oxamides would decompose due to the cleavage of the C–N bonds in oxamide structures,which could be proved by the fragments detected by HR-MS,^(1)H NMR,and the generation of NH_(3)after the reduction of oxamide by Li.This work provides a strategy to deeply understand the charge storage mechanism of organic electrode materials and will stimulate the further development of characterization techniques to reveal the charge storage mechanism for developing high-performance electrode materials.

Catalytic effect in lithium metal batteries: From heterogeneous catalyst to homogenous catalyst

Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.

Hyphae-mediated bioassembly of carbon fibers derivatives for advanced battery energy storage

Ingenious design and fabrication of advanced carbon-based sulfur cathodes are extremely important to the development of high-energy lithium-sulfur batteries,which hold promise as the next-generation power source.Herein,for the first time,we report a novel versatile hyphae-mediated biological assembly technology to achieve scale production of hyphae carbon fibers(HCFs)derivatives,in which different components including carbon,metal compounds,and semiconductors can be homogeneously assembled with HCFs to form composite networks.The mechanism of biological adsorption assembly is also proposed.As a representative,reduced graphene oxides(rGOs)decorated with hollow carbon spheres(HCSs)successfully co-assemble with HCFs to form HCSs@rGOs/HCFs hosts for sulfur cathodes.In this unique architecture,not only large accommodation space for sulfur but also restrained volume expansion and fast charge transport paths are realized.Meanwhile,multiscale physical barriers plus chemisorption sites are simultaneously established to anchor soluble lithium polysulfides.Accordingly,the designed HCSs@rGOs/HCFs-S cathodes deliver a high capacity(1189 mA h g^(-1)at 0.1 C)and good high-rate capability(686 mA h g^(-1)at 5 C).Our work provides a new approach for the preparation of high-performance carbon-based electrodes for energy storage devices.

Polymer engineering for electrodes of aqueous zinc ion batteries

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.

Structural Isomers:Small Change with Big Difference in Anion Storage

Organic electrode materials are promising for batteries.However,the reported organic electrodes are often facing the challenges of low specific capacity,low voltage,poor rate capability and vague charge storage mechanisms,etc.Isomers are good platform to investigate the charge storage mechanisms and enhance the performance of batteries,which,however,have not been focused in batteries.Herein,two isomers are reported for batteries.As a result,the isomer tetrathiafulvalene(TTF)could store two monovalent anions reversibly,deriving an average discharge voltage of 1.05 V and a specific capacity of 220 mAh g−1 at a current density of 2 C.On the other hand,the other isomer tetrathianaphthalene could only reversibly store one monovalent anion and upon further oxidation,it would undergo an irreversible solid-state molecular rearrangement to TTF.The molecular rearrangement was confirmed by electrochemical performances,X-ray diffraction patterns,nuclear magnetic resonance spectra,and 1H detected heteronuclear multiple bond correlation spectra.These results suggested the small structural change could lead to a big difference in anion storage,and we hope this work will stimulate more attention to the structural design for boosting the performance of organic batteries.

A Review of Rechargeable Zinc-Air Batteries:Recent Progress and Future Perspectives

Zinc-air batteries(ZABs)are gaining attention as an ideal option for various applications requiring high-capacity batteries,such as portable electronics,electric vehicles,and renewable energy storage.ZABs offer advantages such as low environmental impact,enhanced safety compared to Li-ion batteries,and cost-effectiveness due to the abundance of zinc.However,early research faced challenges due to parasitic reactions at the zinc anode and slow oxygen redox kinetics.Recent advancements in restructuring the anode,utilizing alternative electrolytes,and developing bifunctional oxygen catalysts have significantly improved ZABs.Scientists have achieved battery reversibility over thousands of cycles,introduced new electrolytes,and achieved energy efficiency records surpassing 70%.Despite these achievements,there are challenges related to lower power density,shorter lifespan,and air electrode corrosion leading to performance degradation.This review paper discusses different battery configurations,and reaction mechanisms for electrically and mechanically rechargeable ZABs,and proposes remedies to enhance overall battery performance.The paper also explores recent advancements,applications,and the future prospects of electrically/mechanically rechargeable ZABs.

An in-situ self-etching enabled high-power electrode for aqueous zinc-ion batteries

Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.

A dual redox-active and robust polymer enables ultrafast and durable proton-storage capability

Aqueous proton batteries(APBs) offer a viable and attractive option in the field of affordable and sustainable energy solutions.Organic polymers are highly favored due to their environmentally friendly manufacturability and malleable molecular configurations,making them suitable materials for constructing APB electrodes.Nonetheless,their currently limited capacity for proton-associated redox reactions poses a challenge to the widespread usage.Herein,we have developed a highly redox-active organic polymer(PTA) tailored for APB applications.The inclusion of dual redox-active moieties in the extended nconjugated frameworks not only enhances the redox activity and refines the electronic properties,but also ensures the high structural integrity of the PTA polymer.When used as an electrode,the PTA polymer has a notable ability to store protons,with a large capacity of 213.99 mA h g^(-1) at 1 A g^(-1) and exceptional long-term stability,as evidenced by retaining 94.6% of its initial capacity after 20,000 cycles.In situ techniques alongside theoretical calculations have unveiled efficient redox processes occurring at C=N and C=O redox-active sites within the PTA electrode upon proton uptake/removal.Furthermore,a softpackage APB device has been assembled with impressive electrochemical behaviors and excellent operational lifespan,accentuating its significant promise for real-world deployment.

Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

Delving into the dissimilarities in electrochemical performance and underlying mechanisms for sodium and potassium ion storage in N-doped carbon-encapsulated metallic Cu_(2)Se nanocubes

The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.

Stabilization of cathode electrolyte interphase for aqueous zinc-ion batteries

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.

Synergistically constructed lamination-like network of redox-active polyimide and MXene via π-π interactions for aqueous NH_(4)^(+) storage

As a nonmetallic charge carrier,ammonium ion(NH_(4)^(+))has garnered significant attention in the construction of aqueous batteries due to its advantages of low molar mass,small hydration size and rapid diffusion in aqueous solutions.Polymers are a kind of potential electro-active materials for aqueous NH_(4)^(+)storage.However,traditional polymer electrodes are typically created by covering the bulky collectors with excessive additives,which could lead to low volume capacity and unsatisfactory stability.Herein,a nanoparticle-like polyimide(PI)was synthesized and then combined with MXene nanosheets to synergistically construct an additive-free and self-standing PI@MXene composite electrode.Significantly,the redox-active PI nanoparticles are enclosed between conductive MXene flakes to create a 3D lamination-like network that promotes electron transmission,while theπ-πinteractions existing between PI and MXene contribute to the enhanced structural integrity and stability within the composite electrode.As such,it delivers superior aqueous NH_(4)^(+)storage behaviors in terms of a notable specific capacity of 110.7 mA·h·cm^(–3) and a long lifespan with only 0.0064%drop each cycle.Furthermore,in-situ Raman and UV–Vis examinations provide evidence of reversible and stable redox mechanism of the PI@MXene composite electrode during NH_(4)^(+)uptake/removal,highlighting its significance in the area of electrochemical energy storage.

Two-dimensional MOF-based materials:Preparations and applications as electrodes in Li-ion batteries

Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.

Research progress of alkaline earth metal iron-based oxides as anodes for lithium-ion batteries

Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.

Optimized electrochemical ammonia production:From metal-N_(2)/NO_(x) batteries to aqueous metal-NO_(x)^(–) batteries

Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe reaction conditions,leads to substantial energy consumption and environmental pollution.It is thus imperative for NH_(3) synthesis methods to be investigated under more favorable conditions.Synthesis of ammonia by electrocatalysis can effectively reduce the environmental damage and other urgent problems,which is a promising solution.Metal-nitrogen series batteries(M-N batteries),such as metal-nitrogen gas batteries,metal-nitrogen oxide batteries and metal-oxynitride batteries have been regarded recently as an exemplar of concurrent NH_(3) synthesis and energy production.Nonetheless,the large-scale application of these batteries is still limited by numerous challenges are currently existing in building high-efficiency M-N batteries,including poor Faradic efficiency and low NH_(3) yield.Therefore,a comprehensive overview of M-N batteries is offered,specifically focusing on advanced strategies for designing highly efficient cathode catalysts in anticipation of future developments.The metal anodes,cathodic electro-reduction reactions,and design principles are encompassed in the discussion,offering detailed insights to enhance understanding.Mechanisms,feasibility analyses,technoeconomic assessments,device combinations,and comparative evaluations are delved into in the review,contributing to a thorough comprehension of diverse systems and their application potential.Perspectives and opportunities for future research directions are also delineated.

Harnessing eco-friendly additives to manipulate zinc-ion solvation structures towards stable zinc metal batteries

Considerable research efforts have been dedicated to investigating the side reactions and the growth of Zn dendritic in aqueous zinc-ion batteries(AZIBs).The incorporation of organic solvents as additives in electrolytes has yielded highly promising results.Nevertheless,their pervasive use has been hindered by concerns regarding their toxicity,flammability,and economic viability.Herein,we propose the utilization of γ-valerolactone(γ-V),a novel eco-friendly solvent,as an alternative for conventional organic additives to improve the performance of Zn anode.Experimental investigations and theoretical analyses have verified that γ-V additives can diminish the Zn^(2+)-desolvation energy and enhance Zn^(2+) transport kinetics.The adsorbed γ-V molecules modulate the nucleation and diffusion of Zn^(2+),facilitating Zn growth along the(002) crystal plane,thus inhibiting dendrite formation and side reactions.Consequently,the modified electrolyte with 3% γ-V exhibit highly reversible cycling for 2800 h at1 mA cm^(-2) and 1 mA h cm^(-2) in Zn//Zn symmetric cell.The Zn//KVOH coin cells deliver a capacity retention of 74.7% after 1000 cycles at 5 A g^(-1).The Zn//KVOH pouch cells maintain a capacity retention of78.7% over 90 cycles at 3 A g^(-1).Notably,the γ-V additives also effectively alleviate the self-discharge phenomenon.This work provides valuable insights on the development of aqueous zinc-ion batteries with superior safety through the modulation of electrolytes using eco-friendly additives.