The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple ...The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple one-step pyrolysis strategy.The experimental results and density functional theory(DFT)calculation show that the formation of FeCo alloy is conducive to promoting electron transfer,and the introduction of S atom can enhance the interaction between FeCo alloy and carbon substrate,thus inhibiting the migration and agglomeration of particles on the surface of carbon material.The FeCo/SNC catalysts show outstanding performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).FeCo/S-NC shows a high half-wave potential(E_(1/2)=0.8823 V)for ORR and a low overpotential at 10 mA cm^(-2)(E_(j=10)=299 mV)for OER.In addition,compared with Pt/C+RuO_(2) assembled Zn-air battery(ZAB),the FeCo/S-NC assembled ZAB exhibits a larger power density(198.8 mW cm^(-2)),a higher specific capacity(786.1 mA h g_(zn)~(-1)),and ultra-stable cycle performance.These results confirm that the optimized composition and the interfacial interaction between catalyst and carbon substrate synergistically enhance the electrochemical performance.展开更多
Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and ...Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.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
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
The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphen...The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.展开更多
Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electr...Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.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
Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in def...Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.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
基金supported by the National Natural Science Foundation of China(52374301 and 22279030)the Fundamental Research Funds for the Central Universities(N2223037)+1 种基金Hebei Key Laboratory of Dielectric and Electrolyte Functional Material,Northeastern University at Qinhuangdao(HKDEFM2021201)the Performance subsidy fund for the Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(22567627H)。
文摘The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple one-step pyrolysis strategy.The experimental results and density functional theory(DFT)calculation show that the formation of FeCo alloy is conducive to promoting electron transfer,and the introduction of S atom can enhance the interaction between FeCo alloy and carbon substrate,thus inhibiting the migration and agglomeration of particles on the surface of carbon material.The FeCo/SNC catalysts show outstanding performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).FeCo/S-NC shows a high half-wave potential(E_(1/2)=0.8823 V)for ORR and a low overpotential at 10 mA cm^(-2)(E_(j=10)=299 mV)for OER.In addition,compared with Pt/C+RuO_(2) assembled Zn-air battery(ZAB),the FeCo/S-NC assembled ZAB exhibits a larger power density(198.8 mW cm^(-2)),a higher specific capacity(786.1 mA h g_(zn)~(-1)),and ultra-stable cycle performance.These results confirm that the optimized composition and the interfacial interaction between catalyst and carbon substrate synergistically enhance the electrochemical performance.
基金supported by the National Natural Science Foundation of China(U1663225,22293020 and 22293022)the National Key R&D Program of China(2021YFE0115800)+2 种基金the Program for Changjiang Scholars and Innovative Research Team in University(IRT_15R52)of the Chinese Ministry of Educationthe Program of Introducing Talents of Discipline to Universities-Plan 111(B20002)from the Ministry of Science and Technology and the Ministry of Education of Chinathe Belgium-China Governmental Key Cooperation Program WBI-MOST(SUB/2021/IND493971/524448)。
文摘Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.
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financially supported by the National Natural Science Foundation of China(22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(ZR2023MB061).
文摘The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.
基金supported by the financial support of the Guangxi Science and Technology Major Projects(Guike AA23023033)。
文摘Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.
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.
基金financially supported by the National Natural Science Foundation of China (51874197)the Natural Science Foundation of Shanghai (21ZR1429400,22ZR1429700)。
文摘Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.
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.
