Solid-state Al-air battery with an ethanol gel electrolyte

Hydrogel electrolyte is especially suitable for solid-state Al-air batteries targeted for various portable applications, which may, however, lead to continuous Al corrosion during battery standby. To tackle this issue, an ethanol gel electrolyte is developed for Al-air battery for the first time in this work, by using KOH as solute and polyethylene oxide as gelling agent. The ethanol gel is found to effectively inhibit Al corrosion compared with the water gel counterpart, leading to stable Al storage. When assembled into an Al-air battery, the ethanol gel electrolyte achieves a much improved discharge lifetime and specific capacity, which are 5.3 and 4.1 times of the water gel electrolyte at 0.1 mA cm^(-2), respectively.By studying the gel properties, it is found that a lower ethanol purity can improve the battery power output, but at the price of decreased discharge efficiency. On the contrary, a higher polymer concentration will decrease the power output, but can bring extra benefit to the discharge efficiency. As for the gel thickness, a moderate value of 1 mm is preferred to balance the power output and energy efficiency. Finally, to cater the increasing market of flexible electronics, a flexible Al-air battery is developed by impregnating the ethanol gel into a paper substrate, which can function normally even under serious deformation or damage.

Prussian Blue Analogue‑Templated Nanocomposites for Alkali‑Ion Batteries:Progress and Perspective

Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Aligned Ion Conduction Pathway of Polyrotaxane‑Based Electrolyte with Dispersed Hydrophobic Chains for Solid‑State Lithium–Oxygen Batteries

A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.

Sulfolane‑Based Flame‑Retardant Electrolyte for High‑Voltage Sodium‑Ion Batteries

Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.

Photo‑Energized MoS_(2)/CNT Cathode for High‑Performance Li–CO_(2)Batteries in a Wide‑Temperature Range

Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.

Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Porous Organic Cage‑Based Quasi‑Solid‑State Electrolyte with Cavity‑Induced Anion‑Trapping Effect for Long‑Life Lithium Metal Batteries

Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.

Optimization Strategies of Na_(3)V_(2)(PO_(4))_(3) Cathode Materials for Sodium‑Ion Batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.

Synthesis of three-dimensionally ordered porous perovskite type LaMnO_3 for Al-air battery

LaMnO3 catalysts with three-dimensionally ordered holes perovskite structure were prepared via closepacked SiO2 template synthesized by Stober-Frink method. SEM, XRD and BET were employed to characterize the microstructure, phases and specific surface area. CV method was used to the oxygen electrode beha-vior of catalysts. Diameter of the holes was about 330 nm, corresponding to the size of SiO2 template. Full-cell discharge tests were performed on aluminum-air battery fabricated by porous LaMnO3.Results showed that the discharge performance of porous LaMnO3 were 1.54 V, 1.42 V and 1.24 V respectively when the discharge currents were set at 5 mA/cm^2,10 mA/cm^2 and 20 mA/cm^2, respectively, which were higher than that of LaMnO3 prepared by coprecipitation method（1.33 V, 1.09 V, 0.63 V, respectively）.

One-step,in situ formation of WN-W_(2)C heterojunctions implanted on N doped carbon nanorods as efficient oxygen reduction catalyst for metal-air battery

Transition metal nitrides and carbides have attracted intensive attentions in metal-air battery application due to their metallic electron transport behavior and high chemical stability toward the oxygen reduction reaction(ORR).Herein,the polyoxometalate@polyaniline composite derived WN-W_(2)C heterostructured composite(WN-W_(2)C@pDC)has been fabricated through an in situ nitriding-carbonization strategy,with WN-W_(2)C nanoparticles implanted on N doped carbon nanorods.Asfabricated WN-W_(2)C@pDC demonstrates prominent electrocatalytic performance towards ORR and excellent cycling stability in metal-air battery,which possesses positive half-wave potential and large diffusion limiting current density(0.81 V and 5.8 mA·cm^(-2)).Moreover,it demonstrates high peak power density of 157.4 mW·cm^(-2)as Al-air primary cathode and excellent stability at the discharge-charge test(>500 h)of Zn-air secondary battery.The excellent activity and durability of WNW_(2)C@pDC catalyst should be attributed to the combined effect of intimate WN-W_(2)C heterointerfaces,unique embedded nanoparticles structure,and excellent electrical media of N doped carbon,confirmed by a series of contrast experiments.

Battery Separators Functionalized with Edge-Rich MoS2/C Hollow Microspheres for the Uniform Deposition of Li2S in High-Performance Lithium-Sulfur Batteries

As promising energy storage systems,lithium-sulfur(Li-S)batteries have attracted significant attention because of their ultra-high energy densities.However,Li-S battery suffers problems related to the complex phase conversion that occurs during the charge-discharge process,particularly the deposition of solid Li2S from the liquid-phase polysulfides,which greatly limits its practical application.In this paper,edge-rich MoS2/C hollow microspheres(Edg-MoS2/C HMs)were designed and used to functionalize separator for Li-S battery,resulting in the uniform deposition of Li2S.The microspheres were fabricated through the facile hydrothermal treatment of MoO3-aniline nanowires and a subsequent carbonization process.The obtained Edg-MoS2/C HMs have a strong chemical absorption capability and high density of Li2S binding sites,and exhibit excellent electrocatalytic performance and can effectively hinder the polysulfide shuttle effect and guide the uniform nucleation and growth of Li2S.Furthermore,we demonstrate that the Edg-MoS2/C HMs can effectively regulate the deposition of Li2S and significantly improve the reversibility of the phase conversion of the active sulfur species,especially at high sulfur loadings and high C-rates.As a result,a cell containing a separator functionalized with Edg-MoS2/C HMs exhibited an initial discharge capacity of 935 mAh g-1 at 1.0 C and maintained a capacity of 494 mAh g-1 after 1000 cycles with a sulfur loading of 1.7 mg cm-2.Impressively,at a high sulfur loading of 6.1 mg cm-2 and high rate of 0.5 C,the cell still delivered a high reversible discharge capacity of 478 mAh g-1 after 300 cycles.This work provides fresh insights into energy storage systems related to complex phase conversions.

Recent progress in rechargeable alkali metal-air batteries

Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.

Concurrent recycling chemistry for cathode/anode in spent graphite/LiFePO_(4) batteries:Designing a unique cation/anion-co-workable dual-ion battery

With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs has become an urge nt task to be solved,otherwise it will inevitably lead to serious environmental pollution.Herein,a unique recycling strategy is proposed to achieve the concurrent reuse of cathode and anode in the spent graphite/LiFePO_(4) batteries.Along with such recycling process,a unique cathode composed of recycled LFP/graphite(RLFPG)with cation/anion-co-storage ability is designed for new-type dual-ion battery(DIB).As a result,the recycle-derived DIB of Li/RLFPG is established with good electrochemical performance,such as an initial discharge capacity of 117.4 mA h g^(-1) at 25 mA g^(-1) and 78% capacity retention after 1000 cycles at 100 mA g^(-1).The working mechanism of Li/RLFPG DIB is also revealed via in situ X-ray diffraction and electrode kinetics studies.This work not only presents a farreaching significance for large-scale recycling of spent LIBs in the future,but also proposed a sustainable and econo mical method to design n ew-type sec on dary batteries as recycling of spe nt LIBs.

Hybrid battery integrated by Zn-air and Zn-Co3O4 batteries at cell level

The construction of Zn based hybrid battery through the combination of Zn-air and Zn-Co3O4 batteries at cell level is a feasible strategy to integrate high voltage,specific capacity and energy density in one power supply equipment.For Zn based hybrid battery,an efficient cathode material with high specific capacitance and excellent ORR,OER activities is a vital component,which determines its performance in great extent.In this work,with Co based coordination polymer as precursor,oxygen vacancy-rich Co3 O4 based cathode material is synthesized.In this material Co3O4 particles with the size about 20 to 35 nm reside evenly in mesoporous carbon matrix doped by nitrogen atoms.In OER,the overpotential of this cathode material is merely 330 m V.Its ORR proceeds with a typical four electron process with half wave achieving 0.76 V.If charge/discharge at 1 A·g^-1,specific capacitance of this cathode material is 254.4 mAh·g^-1.As current density increases to 20 A·g^-1,the specific capacitance still arrives at 122.5 mAh·g^-1 with nearly 50%retained.Based on attractive performance of this cathode material,Zn based hybrid battery is assembled.When discharge at 1 m A·cm-2,it presences two voltage platforms at 1.71 and 1.14 V.In this situation,specific capacitance reaches 790 m Ah·g^-1 with energy density 928 Wh·kg^-1.Hybrid battery shows promising stability after 300-cycle continuous test.

Micro-nanostructural designs of bifunctional electrocatalysts for metal-air batteries

Water-based rechargeable metal-air batteries play an important role in the storage and conversion of renewable electric energy.However,the sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)have limited the practical application of rechargeable metal-air batteries.Most of reviews were focused on single functional electrocatalysts while few on bifunctional electrocatalysts.It is indispensable but challenging to design a bifunctional electrocatalyst that is active and stable to the two reactions.Recently,attempts to develop high active bifunctional electrocatalysts for both ORR and OER increase rapidly.Much work is focused on the micro-nano design of advanced structures to improve the performance of bifunctional electrocatalyst.Transition-metal materials,carbon materials and composite materials,and the methods developed to prepare micro-nano structures,such as electrochemical methods,chemical vapor deposition,hydrothermal methods and template methods are reported in literatures.Additionally,many strategies,such as adjustments of electronic structures,oxygen defects,metal-oxygen bonds,interfacial strain,nano composites,heteroatom doping etc.,have been used extensively to design bifunctional electrocatalysts.To well understand the achievements in the recent literatures,this review focuses on the micro-nano structural design of materials,and the related methods and strategies are classed into two groups for the improvement of intrinsic and apparent activities.The fine adjustment of nano structures and an in-depth understanding of the reaction mechanism are also discussed briefly.

Recent advances in solid-state metal-air batteries

Solid-state metal-air batteries have emerged as a research hotspot due to their high energy density and high safety.Moreover,side reactions caused by infiltrated gases(O_(2),H_(2)O,or CO_(2))and safety issues caused by liquid electrolyte leakage will be eliminated radically.However,the solid-state metal–air battery is still in its infancy,and many thorny problems still need to be solved,such as the large resistance of the metal/electrolyte interface and catalyst design.This review will summarize some important progress and key issues for solid-state metal-air batteries,especially the lithium-,sodium-,and zinc-based metal-air batteries,clarify some core issues,and forecast the future direction of the solid-state metal-air batteries.

Recent advances and perspectives of metal/covalent-organic frameworks in metal-air batteries

Metal-air batteries(MABs)have attracted considerable attention as a novel energy technology that can alleviate the severe energy crisis and environmental pollution.Two primary processes,including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)occur on the air cathode and dominate the battery performance during battery charging and discharging.Recently,metal-organic frameworks(MOFs)and covalent-organic frameworks(COFs)emerge as promising cathode catalysts due to their structure and composition superiority.The unique characteristics of MOFs and COFs contribute to improved performance.This review mainly summarizes the recent applications of MOFs and COFs in a series of MABs,mainly including lithium-and zinc-air batteries.Additionally,some critical issues are emphasized regarding MOFs and COFs used in other MABs limited progress,their fabrication and alternatives to potential problems.