Zinc-air batteries(ZABs)are promising energy storage systems because of high theoretical energy density,safety,low cost,and abundance of zinc.However,the slow multi-step reaction of oxygen and heavy reliance on noble-...Zinc-air batteries(ZABs)are promising energy storage systems because of high theoretical energy density,safety,low cost,and abundance of zinc.However,the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs.Therefore,feasible and advanced non-noble-metal elec-trocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction.In this review,we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field.Then,we discussed the work-ing mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design,crystal structure tuning,interface strategy,and atomic engineering.We also included theoretical studies,machine learning,and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions.Finally,we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.展开更多
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 advant...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.展开更多
Fabricating non-noble metal-based carbon air electrodes with highly efficient bifunctionality is big challenge owing to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).The efficient cathode catal...Fabricating non-noble metal-based carbon air electrodes with highly efficient bifunctionality is big challenge owing to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).The efficient cathode catalyst is urgently needed to further improve the performance of rechargeable zinc-air batteries.Herein,an activation-doping assisted interface modification strategy is demonstrated based on freestanding integrated carbon composite(CoNiLDH@NPC)composed of wood-based N and P doped active carbon(NPC)and CoNi layer double hydroxides(CoNiLDH).In the light of its large specific surface area and unique defective structure,CoNiLDH@NPC with strong interfacecoupling effect in 2D-3D micro-nanostructure exhibits outstanding bifunctionality.Such carbon composites show half-wave potential of 0.85 V for ORR,overpotential of 320 mV with current density of 10 mA cm^(-2) for OER,and ultra-low gap of 0.70 V.Furthermore,highly-ordered open channels of wood provide enormous space to form abundant triple-phase boundary for accelerating the catalytic process.Consequently,zinc-air batteries using CoNiLDH@NPC show high power density(aqueous:263 mW cm^(-2),quasi-solid-state:65.8 mW cm^(-2))and long-term stability(aqueous:500 h,quasi-solid-state:120 h).This integrated protocol opens a new avenue for the rational design of efficient freestanding air electrode from biomass resources.展开更多
The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with e...The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.展开更多
Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity...Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity due to the weak adsorption ability to O-containing species.Here,the S-doped VN anchored on N,S-doped multi-dimensional carbon(S-VN/Co/NS-MC)was constructed using the solvothermal and in-situ doping methods.Incorporating sulfur atoms into VN species alters the electron spin state of vanadium in the S-VN/Co/NS-MC for regulating the adsorption energy of vanadium sites to oxygen molecules.The introduced sulfur atoms polarize the V 3d_(z)^(2) electrons,shifting spin-down electrons closer to the Fermi level in the S-VN/Co/NS-MC.Consequently,the introduction of sulfur atoms into VN species enhances the adsorption energy of vanadium sites for oxygen molecules.The*OOH dissociation transitions from being unspontaneous on the VN surface to a spontaneous state on the S-doped VN surface.Then,the ORR barrier on the S-VN/Co/NS-MC surface is reduced.The S-VN/Co/NS-MC demonstrates a higher half-wave potential and limiting current density compared to the VN/Co/N-MC.The S-VN/Co/NS-MC-based liquid ZABs display a power density of 195.7 m W cm^(-2),a specific capacity of 815.7 m A h g^(-1),and a cycling stability exceeding 250 h.The S-VN/Co/NS-MC-based flexible ZABs are successfully employed to charge both a smart watch and a mobile phone.This approach holds promise for advancing the commercial utilization of VN-based catalysts in ZABs.展开更多
It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxide...It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.展开更多
Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic framewo...Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic frameworks(MOFs)derivatives have been widely studied as oxygen electrocatalysts in ZABs.To date,many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs.In this review,the latest progress of the MOF-derived non-noble metal-oxygen electrocatalysts in ZABs is reviewed.The performance of these MOF-derived catalysts toward oxygen reduction,and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials,single-atom catalysts,metal cluster/carbon composites and metal compound/carbon composites.Moreover,we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal-oxygen electrocatalysts and their structure-performance relationship.Finally,the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.展开更多
The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries...The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries and regenerative fuel cells.Here we report facile synthesis of three-dimensional(3 D)carbon nanotube(CNT)/carbon composites using earth-abundant coal as the carbon source,hydrogen reductant and heteroatom dopant to grow CNTs.The prepared composite featuring 3 D structural merits and multiple active sites can efficiently catalyze both ORR and OER,affording high activity,fast kinetics,and long-term stability.With the additional incorporation of manganese,the developed catalyst afforded a potential difference of 0.80 V between ORR at the half wave potential and OER at a current density of 10 mA cm^(-2).The optimized sample has presented excellent OER performance within a constructed solar-powered water splitting system with continuously generating oxygen bubbles at anode.Notably,it can be further used as a durable air-electrode catalyst in constructed Zn-air battery,delivering an initial discharge/charge voltage gap of 0.73 V,a remained voltaic efficiency of 61.2%after 160 cycles and capability to power LED light for at least 80 h.This study provides an efficient approach for converting traditional energy resource i.e.coal to value-added alternative oxygen electrocatalysts in renewable energy conversion systems.展开更多
Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bif...Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.展开更多
The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in ...The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in the multi-dimensional nitrogen-doped carbon structure(S-FeWO_(4)/NC)was successfully synthesized.The doped S atoms optimized the charge distribution in FeWO_(4)and enhanced the intrinsic activity.At the same time,S doping accelerated the formation of reaction intermediates during the adsorption reduction of O_(2)on the surface of S-FeWO_(4)/NC.Accordingly,the S-FeWO_(4)/NC catalyst showed more positive half-wave potential(0.85 V)and better stability than that of the FeWO_(4)/NC catalyst.Furthermore,the S-FeWO_(4)/NC-based zinc-air battery exhibited considerable power density of 150.3m W cm^(-2),high specific capacity of 912.7 m A h g^(-1),and prominent cycle stability up to 220 h.This work provides an assistance to the development of cheap and efficient tungsten-based oxygen reduction catalysts and the promotion of its application in the zinc-air battery.展开更多
The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient s...The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.展开更多
There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNT...There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.展开更多
Rechargeable zinc-air batteries(ZAB)with a high theoretical energy density of 1086 Wh kg^(-1),have received tremendous research attention.However,the practical application of ZABs is still limited by high polarization...Rechargeable zinc-air batteries(ZAB)with a high theoretical energy density of 1086 Wh kg^(-1),have received tremendous research attention.However,the practical application of ZABs is still limited by high polarization and poor energy efficiency(low power density)due to the sluggish 4 electrons(e^(-))/oxygen(O_(2))kinetics over the air electrode.Here,a noble-metal-free Fe Nx C electrocatalyst is developed via a onepot approach,which provides a high density of the oxygen reduction reaction(ORR)active site and facilitates the ORR kinetics.Accordingly,the as-assembled Zn-air battery displayed a low charge–discharge voltage gap of 0.71 V at 10 m A cm^(-2),a remarkable peak power density as high as 181.2 m W cm^(-2),as well as the long-term durability for hundreds of hours,among the top level of those reported previously.Our work provides a major boost for the practical application of Zn-air battery in the future.展开更多
The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous comp...The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous composite(Ru/HfO_(2)-NC)with Ru/HfO2nanoparticles nested in nitrogen-doped porous carbon via a zeolitic imidazole frameworks-assisted(ZIF)co-precipitation and calcination approach.In particular,ZIF guides an in-situ construction of nested configuration and confines the scattered nanoparticles.Strikingly,Ru/HfO_(2)-NC exhibits unusual ORR activity,superb durability,and methanol tolerance in0.1 M KOH solution with high half-wave potential(E1/2)of 0.83 V and follows a near-4e-reaction pathway.Additionally,the ZAB assembled with cathodic Ru/HfO_(2)-NC outputs a power density of 157.3 m W cm^(-2),a specific capacity of 775 mA h g-1Zn,and a prolonged lifespan of 258 h at 5 mA cm^(-2).Meanwhile,the catalyst has demonstrated potential applicability in flexible ZAB.As suggested by experimental results and density functional theory(DFT)analysis,the remarkable property possibly originated from the optimization of the adsorption and desorption of reactive intermediates caused by the reconfiguration of the electronic structure between Ru and HfO_(2).展开更多
The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assiste...The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.展开更多
Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes h...Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ZAB.Herein,the N-doped carbon cloth(NC)prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite growth.Results show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn^(2+)by boosting the desolvation process of Zn^(2+),eventually reducing the nucleation overpotential.Besides,theoretical calculation results confirm the zincophilicity of N-containing functional group(such as pyridine N and pyrrole N),which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn^(2+) in the vicinity of the surface and enhancing its interaction with zinc atoms.As a result,the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8%and long-term stability of over 500 cycles at 0.2 mA cm^(-2).And the Coulombic efficiency reached about 99.5%at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm^(-2).The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 mV.In addition,the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh g_(Zn)^(-1) and a long life of over 430 cycles.The effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn^(2+) presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.展开更多
Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient...Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.展开更多
Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among...Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among them,flexible solid-state zinc-air batteries have received widespread attention because of their high energy density,good safety,and stability.Efficient bifunctional oxygen electrocatalysts are the primary consideration in the development of flexible solid-state zinc-air batteries,and self-supported air cathodes are strong candidates because of their advantages including simplified fabrication process,reduced interfacial resistance,accelerated electron transfer,and good flexibility.This review outlines the research progress in the design and construction of nanoarray bifunctional oxygen electrocatalysts.Starting from the configuration and basic principles of zinc-air batteries and the strategies for the design of bifunctional oxygen electrocatalysts,a detailed discussion of self-supported air cathodes on carbon and metal substrates and their uses in flexible zinc-air batteries will follow.Finally,the challenges and opportunities in the development of flexible zinc-air batteries will be discussed.展开更多
基金the Natural Science Foundation of China(Grant No:22309180)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No:XDB0600000,XDB0600400)+3 种基金Liaoning Binhai Laboratory,(Grant No:LILBLB-2023-04)Dalian Revitalization Talents Program(Grant No:2022RG01)Youth Science and Technology Foundation of Dalian(Grant No:2023RQ015)the University of Waterloo.
文摘Zinc-air batteries(ZABs)are promising energy storage systems because of high theoretical energy density,safety,low cost,and abundance of zinc.However,the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs.Therefore,feasible and advanced non-noble-metal elec-trocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction.In this review,we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field.Then,we discussed the work-ing mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design,crystal structure tuning,interface strategy,and atomic engineering.We also included theoretical studies,machine learning,and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions.Finally,we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.
基金S.J.Park acknowledges the support from the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.2022M3J7A1062940 and 2023R1A2C1004109)K.H.acknowledges the support from the Ministry of Education of the Republic of Korea and the National Research Foundation of Korea.(NRF-2023R1A2C2008017)+1 种基金Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2020R1A6A1A03043435)The authors extend their appreciation to the Researchers Supporting Project(RSP2024R381),King Saud University,Riyadh,Saudi Arabia.
文摘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.
基金financially supported by the National Key Research and Development Program of China(2022YF E0138900)National Natural Science Foundation of China(21972017)+2 种基金the Fundamental Research Funds for the Central Universities(2232022D-18)Shanghai Sailing Program(22YF1400700)the Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22CGA37).
文摘Fabricating non-noble metal-based carbon air electrodes with highly efficient bifunctionality is big challenge owing to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).The efficient cathode catalyst is urgently needed to further improve the performance of rechargeable zinc-air batteries.Herein,an activation-doping assisted interface modification strategy is demonstrated based on freestanding integrated carbon composite(CoNiLDH@NPC)composed of wood-based N and P doped active carbon(NPC)and CoNi layer double hydroxides(CoNiLDH).In the light of its large specific surface area and unique defective structure,CoNiLDH@NPC with strong interfacecoupling effect in 2D-3D micro-nanostructure exhibits outstanding bifunctionality.Such carbon composites show half-wave potential of 0.85 V for ORR,overpotential of 320 mV with current density of 10 mA cm^(-2) for OER,and ultra-low gap of 0.70 V.Furthermore,highly-ordered open channels of wood provide enormous space to form abundant triple-phase boundary for accelerating the catalytic process.Consequently,zinc-air batteries using CoNiLDH@NPC show high power density(aqueous:263 mW cm^(-2),quasi-solid-state:65.8 mW cm^(-2))and long-term stability(aqueous:500 h,quasi-solid-state:120 h).This integrated protocol opens a new avenue for the rational design of efficient freestanding air electrode from biomass resources.
基金the financial support of the National Natural Science Foundation of China(52002079,22378074,22179025 and U20A20340)the Guangdong Basic and Applied Basic Research Foundation(2022A1515140085)+2 种基金the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202209)the Guangzhou Hongmian Project(HMJH-20200012)the Foshan Introducing Innovative and Entrepreneurial Teams(1920001000108)。
文摘The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22178148,22278193,22075113)the Jiangsu Province and Education Ministry Co-Sponsored Synergistic Innovation Center of Modern Agricultural Equipment(Grant No.XTCX2029)+1 种基金a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Postgraduate Research&Practice Innovation Program of Jiangsu Province(Grant No.KYCX22_3691)。
文摘Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity due to the weak adsorption ability to O-containing species.Here,the S-doped VN anchored on N,S-doped multi-dimensional carbon(S-VN/Co/NS-MC)was constructed using the solvothermal and in-situ doping methods.Incorporating sulfur atoms into VN species alters the electron spin state of vanadium in the S-VN/Co/NS-MC for regulating the adsorption energy of vanadium sites to oxygen molecules.The introduced sulfur atoms polarize the V 3d_(z)^(2) electrons,shifting spin-down electrons closer to the Fermi level in the S-VN/Co/NS-MC.Consequently,the introduction of sulfur atoms into VN species enhances the adsorption energy of vanadium sites for oxygen molecules.The*OOH dissociation transitions from being unspontaneous on the VN surface to a spontaneous state on the S-doped VN surface.Then,the ORR barrier on the S-VN/Co/NS-MC surface is reduced.The S-VN/Co/NS-MC demonstrates a higher half-wave potential and limiting current density compared to the VN/Co/N-MC.The S-VN/Co/NS-MC-based liquid ZABs display a power density of 195.7 m W cm^(-2),a specific capacity of 815.7 m A h g^(-1),and a cycling stability exceeding 250 h.The S-VN/Co/NS-MC-based flexible ZABs are successfully employed to charge both a smart watch and a mobile phone.This approach holds promise for advancing the commercial utilization of VN-based catalysts in ZABs.
基金the financial support from the National Natural Science Foundation of China (51872067 and 21773048)
文摘It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.
基金This work is supported by the National Natural Science Foundation of China(22075092)the Program for HUST Academic Frontier Youth Team(2018QYTD15).
文摘Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic frameworks(MOFs)derivatives have been widely studied as oxygen electrocatalysts in ZABs.To date,many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs.In this review,the latest progress of the MOF-derived non-noble metal-oxygen electrocatalysts in ZABs is reviewed.The performance of these MOF-derived catalysts toward oxygen reduction,and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials,single-atom catalysts,metal cluster/carbon composites and metal compound/carbon composites.Moreover,we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal-oxygen electrocatalysts and their structure-performance relationship.Finally,the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.
基金The financial supports from the National Natural Science Foundation of China(21605067,21763023)Talent Project Grant of the University of Science and Technology Liaoning(601011507-06)Doctoral Start-up Research Funding of the University of Science and Technology Liaoning(USTL010178),China。
文摘The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries and regenerative fuel cells.Here we report facile synthesis of three-dimensional(3 D)carbon nanotube(CNT)/carbon composites using earth-abundant coal as the carbon source,hydrogen reductant and heteroatom dopant to grow CNTs.The prepared composite featuring 3 D structural merits and multiple active sites can efficiently catalyze both ORR and OER,affording high activity,fast kinetics,and long-term stability.With the additional incorporation of manganese,the developed catalyst afforded a potential difference of 0.80 V between ORR at the half wave potential and OER at a current density of 10 mA cm^(-2).The optimized sample has presented excellent OER performance within a constructed solar-powered water splitting system with continuously generating oxygen bubbles at anode.Notably,it can be further used as a durable air-electrode catalyst in constructed Zn-air battery,delivering an initial discharge/charge voltage gap of 0.73 V,a remained voltaic efficiency of 61.2%after 160 cycles and capability to power LED light for at least 80 h.This study provides an efficient approach for converting traditional energy resource i.e.coal to value-added alternative oxygen electrocatalysts in renewable energy conversion systems.
基金This work is supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)Centre Québéco is sur les Materiaux Fonctionnels(CQMF),Fonds de Recherche du Québec-Nature et Technologies(FRQNT)+2 种基金Institut National de la Recherche Scientifique(INRS)This work is also supported by the National Natural Science Foundation of China(21972017)the“Scientific and Technical Innovation Action Plan”Hong Kong,Macao and Taiwan Science&Technology Cooperation Project of Shanghai Science and Technology Committee(19160760600).F.Dong gratefully acknowledges scholarships from the China Scholarship Council(CSC).
文摘Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.
基金the support of the National Natural Science Foundation of China(Nos.22178148,U21A20328)the Natural Science Foundation of Jiangsu Province(No.BK20191430)+2 种基金the Six Talent Peaks Project in Jiangsu Province(No.XNY-009)the Jiangsu Province and Education Ministry CoSponsored Synergistic Innovation Center of Modern Agricultural Equipment(No.XTCX2029)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in the multi-dimensional nitrogen-doped carbon structure(S-FeWO_(4)/NC)was successfully synthesized.The doped S atoms optimized the charge distribution in FeWO_(4)and enhanced the intrinsic activity.At the same time,S doping accelerated the formation of reaction intermediates during the adsorption reduction of O_(2)on the surface of S-FeWO_(4)/NC.Accordingly,the S-FeWO_(4)/NC catalyst showed more positive half-wave potential(0.85 V)and better stability than that of the FeWO_(4)/NC catalyst.Furthermore,the S-FeWO_(4)/NC-based zinc-air battery exhibited considerable power density of 150.3m W cm^(-2),high specific capacity of 912.7 m A h g^(-1),and prominent cycle stability up to 220 h.This work provides an assistance to the development of cheap and efficient tungsten-based oxygen reduction catalysts and the promotion of its application in the zinc-air battery.
基金supported by the Beijing Natural Science Foundation (2222004)。
文摘The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.
基金financial support from the National Natural Science Foundation of China (U1510120, 91645110)the Project of Introducing Overseas Intelligence High Education of China (2017-2018)+1 种基金the Graduate Thesis Innovation Foundation of Donghua University (EG2016034)the College of Environmental Science and Engineering, State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University
文摘There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.
基金financially supported by the Shenzhen Science and Technology Research Grant(JCYJ20200109140416788)the Chemistry and Chemical Engineering Guangdong Laboratory(1922018)+1 种基金the National Key R&D Program of China(2020YFB0704500)the financial support from the China Scholarship Council(CSC)and the Australian Research Council(ARC)through an ARC project(ARC DP160102627 and ARC DP170101467)。
文摘Rechargeable zinc-air batteries(ZAB)with a high theoretical energy density of 1086 Wh kg^(-1),have received tremendous research attention.However,the practical application of ZABs is still limited by high polarization and poor energy efficiency(low power density)due to the sluggish 4 electrons(e^(-))/oxygen(O_(2))kinetics over the air electrode.Here,a noble-metal-free Fe Nx C electrocatalyst is developed via a onepot approach,which provides a high density of the oxygen reduction reaction(ORR)active site and facilitates the ORR kinetics.Accordingly,the as-assembled Zn-air battery displayed a low charge–discharge voltage gap of 0.71 V at 10 m A cm^(-2),a remarkable peak power density as high as 181.2 m W cm^(-2),as well as the long-term durability for hundreds of hours,among the top level of those reported previously.Our work provides a major boost for the practical application of Zn-air battery in the future.
基金supported by the National Natural Science Foundation of China(21965005)the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001)+1 种基金the Project of HighLevel Talents of Guangxi(F-KA18015)Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。
文摘The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous composite(Ru/HfO_(2)-NC)with Ru/HfO2nanoparticles nested in nitrogen-doped porous carbon via a zeolitic imidazole frameworks-assisted(ZIF)co-precipitation and calcination approach.In particular,ZIF guides an in-situ construction of nested configuration and confines the scattered nanoparticles.Strikingly,Ru/HfO_(2)-NC exhibits unusual ORR activity,superb durability,and methanol tolerance in0.1 M KOH solution with high half-wave potential(E1/2)of 0.83 V and follows a near-4e-reaction pathway.Additionally,the ZAB assembled with cathodic Ru/HfO_(2)-NC outputs a power density of 157.3 m W cm^(-2),a specific capacity of 775 mA h g-1Zn,and a prolonged lifespan of 258 h at 5 mA cm^(-2).Meanwhile,the catalyst has demonstrated potential applicability in flexible ZAB.As suggested by experimental results and density functional theory(DFT)analysis,the remarkable property possibly originated from the optimization of the adsorption and desorption of reactive intermediates caused by the reconfiguration of the electronic structure between Ru and HfO_(2).
基金financial support from the National Key Research and Development Project (2017YFB0308200)the CAS Key Laboratory of Carbon Materials (KLCMKFJJ2011)。
文摘The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.
基金supported by the National Natural Science Foundation of China(Grant No.21905033)the Science and Technology Department of Sichuan Province(Grant No.2019YJ0503)State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2020P4FZG02A).
文摘Aqueous zinc-air battery(ZAB)has attractive features as the potential energy storage system such as high safety,low cost and good environmental compatibility.However,the issue of dendrite growth on zinc metal anodes has seriously hindered the development of ZAB.Herein,the N-doped carbon cloth(NC)prepared via magnetron sputtering is explored as the substrate to induce the uniform nucleation of zinc metal and suppress dendrite growth.Results show that the introduction of heteroatoms accelerates the migration and deposition kinetics of Zn^(2+)by boosting the desolvation process of Zn^(2+),eventually reducing the nucleation overpotential.Besides,theoretical calculation results confirm the zincophilicity of N-containing functional group(such as pyridine N and pyrrole N),which can guide the nucleation and growth of zinc uniformly on the electrode surface by both promoting the redistribution of Zn^(2+) in the vicinity of the surface and enhancing its interaction with zinc atoms.As a result,the half-cell assembled with magnetron sputtered carbon cloth achieves a high zinc stripping/plating coulombic efficiency of 98.8%and long-term stability of over 500 cycles at 0.2 mA cm^(-2).And the Coulombic efficiency reached about 99.5%at the 10th cycle and maintained for more than 210 cycles at a high current density of 5.0 mA cm^(-2).The assembled symmetrical battery can deliver 220 plating/stripping cycles with ultra-low voltage hysteresis of only 11 mV.In addition,the assembled zinc-air full battery with NC-Zn anode delivers a high special capacity of about 429 mAh g_(Zn)^(-1) and a long life of over 430 cycles.The effectiveness of surface functionalization in promoting the transfer and deposition kinetics of Zn^(2+) presented in this work shows enlightening significance in the development of metal anodes in aqueous electrolytes.
基金supported by the National Science Foundation of China(21805235)the Opening Foundation of Creative Platform of the Key Laboratory of the Education Department of Hunan Province(20K131)the Construct Program of the Key Discipline in Hunan Province。
文摘Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.
基金supported by the National Natural Science Foundation of China(22072107,21872105)the Natural Science Foundation of Shanghai(23ZR1464800)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Science&Technology Commission of Shanghai Municipality(19DZ2271500)。
文摘Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among them,flexible solid-state zinc-air batteries have received widespread attention because of their high energy density,good safety,and stability.Efficient bifunctional oxygen electrocatalysts are the primary consideration in the development of flexible solid-state zinc-air batteries,and self-supported air cathodes are strong candidates because of their advantages including simplified fabrication process,reduced interfacial resistance,accelerated electron transfer,and good flexibility.This review outlines the research progress in the design and construction of nanoarray bifunctional oxygen electrocatalysts.Starting from the configuration and basic principles of zinc-air batteries and the strategies for the design of bifunctional oxygen electrocatalysts,a detailed discussion of self-supported air cathodes on carbon and metal substrates and their uses in flexible zinc-air batteries will follow.Finally,the challenges and opportunities in the development of flexible zinc-air batteries will be discussed.
