Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely comme...Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely commercial application and development of LSB is mainly hindered by serious“shuttle effect”of lithium polysulfides(Li PSs),slow reaction kinetics,notorious lithium dendrites,etc.In various structures of LSB materials,array structured materials,possessing the composition of ordered micro units with the same or similar characteristics of each unit,present excellent application potential for various secondary cells due to some merits such as immobilization of active substances,high specific surface area,appropriate pore sizes,easy modification of functional material surface,accommodated huge volume change,enough facilitated transportation for electrons/lithium ions,and special functional groups strongly adsorbing Li PSs.Thus many novel array structured materials are applied to battery for tackling thorny problems mentioned above.In this review,recent progresses and developments on array structured materials applied in LSBs including preparation ways,collaborative structural designs based on array structures,and action mechanism analyses in improving electrochemical performance and safety are summarized.Meanwhile,we also have detailed discussion for array structured materials in LSBs and constructed the structure-function relationships between array structured materials and battery performances.Lastly,some directions and prospects about preparation ways,functional modifications,and practical applications of array structured materials in LSBs are generalized.We hope the review can attract more researchers'attention and bring more studying on array structured materials for other secondary batteries including LSB.展开更多
Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properti...Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.展开更多
Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries(SIBs).However,realizing the orientated growth and u...Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries(SIBs).However,realizing the orientated growth and uniform distribution of the heterostructure is still a great challenge.Herein,the regulated novel CoSe_(2)/NiSe_(2)heterostructure confined in N-doped carbon nanofibers(CoSe_(2)/NiSe_(2)@N-C)are prepared by using Co/Ni-ZIF template,in which,the CoSe_(2)/NiSe_(2)heterostructures realize uniform distribution on a micro level.Benefiting from the unique heterostructure and N-doped carbon nanofibers,the CoSe_(2)/NiSe_(2)@N-C deliveries superior rate capability and durable cycle lifespan with a reversible capacity of 400.5 mA h g^(-1)after 5000 cycles at 2 A g^(-1).The Na-ion full battery with CoSe_(2)/NiSe_(2)@N-C anode and layered oxide cathode displays a remarkable energy density of 563 W h kg^(-1)with 241.1 W kg^(-1)at 0.1 A g^(-1).The theoretical calculations disclose that the periodic and directional built-in electric-field along with the heterointerfaces of CoSe_(2)/NiSe_(2)@N-C can accelerate electrochemical reaction kinetics.The in(ex)situ experimental measurements reveal the reversible conversion reaction and stable structure of CoSe_(2)/NiSe_(2)@N-C during Na+insertion/extraction.The study highlights the potential ability of precisely controlled heterostructure to stimulate the electrochemical performances of advanced anode for SIBs.展开更多
The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical cap...Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.展开更多
Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conduct...Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.展开更多
Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structur...Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.展开更多
Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a fa...Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.展开更多
Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory ...Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory cycling performance. Here, we report a porous V2O5 nanofibers cathode with high Znstorage performance in an aqueous Zn(CF3SO3)2 electrolyte. We propose a reaction mechanism based on phase transition from orthorhombic V2O5 to zinc pyrovanadate on first discharging and reversible Zn^2+ (de)intercalation in the open-structured hosts during subsequent cycling. This open and stable architecture enables a high reversible capacity of 319 mAh g^-1 at 20 mAg^-1 and a capacity retention of 81% over 500 cycles. The remarkable electrochemical performance makes V2O5 a promising cathode for aqueous zinc-ion batteries.展开更多
To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surfa...To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.展开更多
In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2F...In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with(NH4)2Fe(SO4)2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃(0.1 C),revealing the potential application in lithium-ion batteries.展开更多
Precise modulation of the structure and composition of electrocatalysts is critical for promoting the kinetically sluggish process of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Covalent organic f...Precise modulation of the structure and composition of electrocatalysts is critical for promoting the kinetically sluggish process of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Covalent organic frameworks(COF)offer a novel way to create highly efficient electrocatalysts due to their tunable composition,structure and surface area.Herein,we report a high-efficiency bifunctional electrocatalyst comprising Co nanoparticles embedded within N-doped carbons(Co@NCs)for Zn-air batteries(ZABs).The Co@NC is yielded via the coordination of a triazine COF with Co-containing precursors and subsequent calcination under inert atmosphere.The as-prepared Co@NC exhibits remarkable ORR/OER performance and great potential in rechargeable ZABs.The liquid ZAB constructed with Co@NC provides both high specific capacity and power density.Remarkably,the ZAB exhibits a voltage gap of 0.8 V during discharge and charge cycles and high stability for 220 h compared to the Pt/C-assembled battery.This strategy for regulating electrocatalytic activities of COF-derived carbon materials could be expanded for creating various carbon catalysts.展开更多
Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated ...Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.展开更多
In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The ...In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The DFT results showed that Ru-N_(x)SACs had the best catalytic performance among the four catalysts,and Ru-N_(x)SACs could effectively inhibit the reduction of ruthenium cation.To verify the DFT results,Ru-N_(x)SACs were fabricated by pyrolyzing MOFs in-situ spatially confined metal precursors.The N coordination environment could be controlled by changing the pyrolysis temperature.Catalytic performance tests indicated that low N coordination number(Ru-N_(2),Ru-N_(3))exhibited excellent catalytic activity and stability compared to RuCl_(3)catalyst.DFT calculations further revealed that Ru-N_(2)and Ru-N_(3)had a tendency to activate HCl at the first step of reaction,whereas Ru-N4tended to activate C_(2)H_(2).These findings will serve as a reference for the design and control of metal active sites.展开更多
High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimensi...High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimension and morphology remains a major challenge.Here,scalable HEO morphology modulation is implemented through a salt-assisted strategy,which is achieved by regulating the solubility of reactants and the selective adsorption of salt ions on specific crystal planes.The electrochemical properties,lithiation mechanism,and structure evolution of composition-and morphology-dependent HEO anode are examined in detail.More importantly,the potential advantages of HEOs as electrode materials are evaluated from both theoretical and experimental aspects.Benefiting from the high oxygen vacancy concentration,narrow band gap,and structure durability induced by the multi-element synergy,HEO anode delivers desirable reversible capacity and reaction kinetics.In particular,Mg is evidenced to serve as a structural sustainer that significantly inhibits the volume expansion and retains the rock salt lattice.These new perspectives are expected to open a window of opportunity to compositionally/morphologi cally engineer high-performance HEO electrodes.展开更多
The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires...The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires a long processing time and an inert atmosphere.Here,a microwave-assisted ultrafast carbonization technique was developed that carbonizes natural wood in seconds without the need for an inert atmosphere,and the obtained aligned-porous carbonized wood provided an excellent electrochemical performance as an anode material for lithium-ion batteries.This ultrafast carbonization technique simultaneously produced ZnO nanoparticles during the carbonization process that were uniformly distributed on the alignedporous carbon.The hierarchical structure of carbonized wood functionalized with ZnO nanoparticles was used as a host for achieving high-performance lithium-sulfur batteries:the highly conductive carbonized wood framework with vertical channels provided good electron transport pathways,and the homogeneously dispersed ZnO nanoparticles effectively adsorbed lithium polysulfide and catalyzed its conversion reactions.In summary,a new method was developed to realize the ultrafast carbonization of biomass materials with decorated metal oxide nanoparticles.展开更多
Among the alloying-type anodes,elemental Sb possesses the suitable yet safe plateau,simple lithiation pathway,small voltage polarization,high conductivity,and superior cycle stability.However,challenge is that its int...Among the alloying-type anodes,elemental Sb possesses the suitable yet safe plateau,simple lithiation pathway,small voltage polarization,high conductivity,and superior cycle stability.However,challenge is that its intrinsic capacity is rather low(660 mAh g^(-1)),<1/6 of silicon.Herein,we propose a seamless integration strategy by merging the voltage and capacity of phosphorus and antimony into a solid solution alloy.Interestingly,the enlistment of P is found greatly enlarge the capacity from 660 to 993 mAh g^(-1) for such Sb_(30)P_(30) solid solution,while maintaining a single and stable discharge plateau(~0.79 V)similar to elemental Sb.Various experimental characterizations including XPS,PDF,Raman,and EDS mapping reveal that in such a material the P and Sb atoms have interacted with each other to form a homogenous solid solution alloy,rather than a simple mixing of the two substances.Thus,the Sb_(30)P_(30) exhibits superior rate performances(807 mAh g^(-1) at 5000 mA g^(-1))and cyclability(821 mAh g^(-1) remained after 300 cycles).Furthermore,such Sb_(60-x)P_(x) alloys can even deliver 621 mAh g^(-1) at30℃,which can be served as the alternative anode materials for high-energy and low-temperature batteries.This unique seamless integration strategy based on solid solution chemistry can be easily leveraged to manipulate the capacity of other electrode materials at similar voltage.展开更多
Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous ba...Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous batteries hinders their practical application.The solvent water freezes at low temperatures,and there is a reduction in ionic conductivity,whereas it evaporates rapidly at high temperatures,which causes increased side reactions.This review discusses recent progress in improving the performance of aqueous batteries,mainly with respect to electrolyte engineering and the associated strategies employed to achieve such improvements over a wide temperature domain.The review focuses on fi ve electrolyte engineer-ing(aqueous high-concentration electrolytes,organic electrolytes,quasi-solid/solid electrolytes,hybrid electrolytes,and eutectic electrolytes)and investigates the mechanisms involved in reducing the solidifi cation point and boiling point of the electrolyte and enhancing the extreme-temperature electrochemical performance.Finally,the prospect of further improving the wide temperature range performance of aqueous rechargeable batteries is presented.展开更多
Li-air batteries have attracted extensive attention because of their ultrahigh theoretical energy density. However, the potential safety hazard of flammable organic liquid electrolytes hinders their practical applicat...Li-air batteries have attracted extensive attention because of their ultrahigh theoretical energy density. However, the potential safety hazard of flammable organic liquid electrolytes hinders their practical applications. Replacing liquid electrolytes with solidstate electrolytes(SSEs) is expected to fundamentally overcome the safety issues. In this work, we focus on the development and challenge of solid-state Li-air batteries(SSLABs). The rise of different types of SSEs, interfacial compatibility and verifiability in SSLABs are presented. The corresponding strategies and prospects of SSLABs are also proposed. In particular, combining machine learning method with experiment and in situ(or operando)techniques is imperative to accelerate the development of SSLABs.展开更多
The development of novel organic electrode materials is of great significance for improving the reversible capacity and cycle stability of rechargeable batteries.Before practical application,it is essential to charact...The development of novel organic electrode materials is of great significance for improving the reversible capacity and cycle stability of rechargeable batteries.Before practical application,it is essential to characterize the electrode materials to study their structures,redox mechanisms and electrochemical performances.In this review,the common characterization methods that have been adopted so far are summarized from two aspects:experimental characterization and theoretical calculation.The experimental characterization is introduced in detail from structural characterization,electrochemical characterization and electrode reaction chara cterization.The experimental purposes and working principles of various experimental characterization methods are briefly illustrated.As the auxilia ry means,theoretical calculation provides the theoretical basis for characterizing the electrochemical reaction mechanism of organic electrode materials.Through these characterizations,we will have a deep understanding about the material structures,electrochemical redox mechanisms,electrochemical properties and the relationships of structure-property.It is hoped that this review would help researchers to select the suitable characterization methods to analyze the structures and performances of organic electrode materials quickly and effectively.展开更多
基金This work was supported by the National Natural Science Foundation of China(52203066,51973157,61904123)the Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金the National innovation and entrepreneurship training program for college students(202310058007)the Tianjin Municipal college students’innovation and entrepreneurship training program(202310058088)the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(Grant No.2018KJ196)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University.
文摘Lithium-sulfur battery(LSB)has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems.The widely commercial application and development of LSB is mainly hindered by serious“shuttle effect”of lithium polysulfides(Li PSs),slow reaction kinetics,notorious lithium dendrites,etc.In various structures of LSB materials,array structured materials,possessing the composition of ordered micro units with the same or similar characteristics of each unit,present excellent application potential for various secondary cells due to some merits such as immobilization of active substances,high specific surface area,appropriate pore sizes,easy modification of functional material surface,accommodated huge volume change,enough facilitated transportation for electrons/lithium ions,and special functional groups strongly adsorbing Li PSs.Thus many novel array structured materials are applied to battery for tackling thorny problems mentioned above.In this review,recent progresses and developments on array structured materials applied in LSBs including preparation ways,collaborative structural designs based on array structures,and action mechanism analyses in improving electrochemical performance and safety are summarized.Meanwhile,we also have detailed discussion for array structured materials in LSBs and constructed the structure-function relationships between array structured materials and battery performances.Lastly,some directions and prospects about preparation ways,functional modifications,and practical applications of array structured materials in LSBs are generalized.We hope the review can attract more researchers'attention and bring more studying on array structured materials for other secondary batteries including LSB.
基金supported by the National Natural Science Foundation of China(21875118,22111530112)the support from the Smart Sensing Interdisciplinary Science Center,Nankai University。
文摘Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2021QB055,ZR2023MB017,ZR2022JQ10)the National Natural Science Foundation of China(21901146,220781792,22274083)。
文摘Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries(SIBs).However,realizing the orientated growth and uniform distribution of the heterostructure is still a great challenge.Herein,the regulated novel CoSe_(2)/NiSe_(2)heterostructure confined in N-doped carbon nanofibers(CoSe_(2)/NiSe_(2)@N-C)are prepared by using Co/Ni-ZIF template,in which,the CoSe_(2)/NiSe_(2)heterostructures realize uniform distribution on a micro level.Benefiting from the unique heterostructure and N-doped carbon nanofibers,the CoSe_(2)/NiSe_(2)@N-C deliveries superior rate capability and durable cycle lifespan with a reversible capacity of 400.5 mA h g^(-1)after 5000 cycles at 2 A g^(-1).The Na-ion full battery with CoSe_(2)/NiSe_(2)@N-C anode and layered oxide cathode displays a remarkable energy density of 563 W h kg^(-1)with 241.1 W kg^(-1)at 0.1 A g^(-1).The theoretical calculations disclose that the periodic and directional built-in electric-field along with the heterointerfaces of CoSe_(2)/NiSe_(2)@N-C can accelerate electrochemical reaction kinetics.The in(ex)situ experimental measurements reveal the reversible conversion reaction and stable structure of CoSe_(2)/NiSe_(2)@N-C during Na+insertion/extraction.The study highlights the potential ability of precisely controlled heterostructure to stimulate the electrochemical performances of advanced anode for SIBs.
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
基金The authors acknowledge the support of the Shenyang University of Technology(QNPY202209-4)the National Natural Science Foundation of China(21571132)+1 种基金Jiangsu University Advanced Talent Fund(5501710002)the Education Department of Liaoning Province(JYTQN2023285).
文摘Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.
基金the National Natural Science Foundation of China(52062012)Key Science&Technology Project of Hainan Province(ZDYF2020028)+2 种基金Key-Area Research and Development Program of Guangdong Province(2019B1102109003)the Innovation Team of Universities of Guangdong Province(2020KCXTD011)Guangdong Province Key Discipline Construction Project(2021ZDJS102).
文摘Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.
基金financially supported by the National Natural Science Foundation of China(22172082,21978137,and 21878162)the Natural Science Foundation of Tianjin(20JCZDJC00770)+1 种基金the NCC Fund(NCC2020FH05)the Fundamental Research Funds for the Central Universities。
文摘Electrochemical CO_(2)reduction to formate is a potential approach to achieving global carbon neutrality.Here,Cu1Bi1bimetallic catalyst was prepared by a co-precipitation method.It has a ginger like composite structure(CuO/CuBi_(2)O_(4))and exhibited a high formate faradaic efficiency of 98.07%at–0.98 V and a large current density of–56.12 mA.cm^(-2)at–1.28 V,which is twice as high as Bi2O3catalyst.Especially,high selectivity(FE^(–)_(HCOO)>85%)is maintained over a wide potential window of 500 mV.In-situ Raman measurements and structure characterization revealed that the reduced Cu1Bi1bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures.The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO_(2)RR,while the Bi-O structures may stabilize the CO_(2)^(*–)intermediate.The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO^(*)pathway.
基金supported by National Natural Science Foundation of China (21773128)。
文摘Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.
基金financially supported by Tianjin Natural Science Foundation (No. 18JCZDJC31100)MOST(2017YFA0206700 and 2016YFA0202503)+1 种基金MOE(B12015)the Fundamental Research Funds for the Central Universities
文摘Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory cycling performance. Here, we report a porous V2O5 nanofibers cathode with high Znstorage performance in an aqueous Zn(CF3SO3)2 electrolyte. We propose a reaction mechanism based on phase transition from orthorhombic V2O5 to zinc pyrovanadate on first discharging and reversible Zn^2+ (de)intercalation in the open-structured hosts during subsequent cycling. This open and stable architecture enables a high reversible capacity of 319 mAh g^-1 at 20 mAg^-1 and a capacity retention of 81% over 500 cycles. The remarkable electrochemical performance makes V2O5 a promising cathode for aqueous zinc-ion batteries.
基金supported by the Natural Science Foundation of Shandong Province(ZR2019PB013)the Natural Science Foundation of Tianjin(19JCZDJC37700)the National Natural Science Foundation of China(21421001 and 21875118)。
文摘To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.
基金supported by the Programs of National 973(2011CB935900)NSFC(21231005)+1 种基金MOE(B12015 and 113016A)the Fundamental Research Funds for the Central Universities
文摘In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with(NH4)2Fe(SO4)2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃(0.1 C),revealing the potential application in lithium-ion batteries.
基金supported by the Natural Science Foundation of Shandong Province(ZR2019PB013)the Training Program of Innovation and Entrepreneurship for Undergraduates of Liaocheng University(CXCY2022277)。
文摘Precise modulation of the structure and composition of electrocatalysts is critical for promoting the kinetically sluggish process of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Covalent organic frameworks(COF)offer a novel way to create highly efficient electrocatalysts due to their tunable composition,structure and surface area.Herein,we report a high-efficiency bifunctional electrocatalyst comprising Co nanoparticles embedded within N-doped carbons(Co@NCs)for Zn-air batteries(ZABs).The Co@NC is yielded via the coordination of a triazine COF with Co-containing precursors and subsequent calcination under inert atmosphere.The as-prepared Co@NC exhibits remarkable ORR/OER performance and great potential in rechargeable ZABs.The liquid ZAB constructed with Co@NC provides both high specific capacity and power density.Remarkably,the ZAB exhibits a voltage gap of 0.8 V during discharge and charge cycles and high stability for 220 h compared to the Pt/C-assembled battery.This strategy for regulating electrocatalytic activities of COF-derived carbon materials could be expanded for creating various carbon catalysts.
基金supported financially by the National Natural Foundation of China(Grant No.51672234)the Research Foundation for Hunan Youth Outstanding People from Hunan Provincial Science and Technology Department(2015RS4030)+1 种基金Hunan 2011 Collaborative Innovation Center of Chemical Engineering&Technology with Environmental Benignity and Effective Resource UtilizationProgram for Innovative Research Cultivation Team in University of Ministry of Education of China(1337304)
文摘Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.
基金supported by the National Natural Science Foundation of China (NSFC,22172082,21978137,22102074,and 21878162)Natural Science Foundation of Tianjin (20JCZDJC00770)+1 种基金Postdoctoral Research Foundation of China (2021M701776)NCC Fund (NCC2020FH05)。
文摘In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The DFT results showed that Ru-N_(x)SACs had the best catalytic performance among the four catalysts,and Ru-N_(x)SACs could effectively inhibit the reduction of ruthenium cation.To verify the DFT results,Ru-N_(x)SACs were fabricated by pyrolyzing MOFs in-situ spatially confined metal precursors.The N coordination environment could be controlled by changing the pyrolysis temperature.Catalytic performance tests indicated that low N coordination number(Ru-N_(2),Ru-N_(3))exhibited excellent catalytic activity and stability compared to RuCl_(3)catalyst.DFT calculations further revealed that Ru-N_(2)and Ru-N_(3)had a tendency to activate HCl at the first step of reaction,whereas Ru-N4tended to activate C_(2)H_(2).These findings will serve as a reference for the design and control of metal active sites.
基金supported by the National Natural Science Foundation of China(52104309,52272021)the Natural Science Foundation of Hubei Province(2021CFB010)。
文摘High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimension and morphology remains a major challenge.Here,scalable HEO morphology modulation is implemented through a salt-assisted strategy,which is achieved by regulating the solubility of reactants and the selective adsorption of salt ions on specific crystal planes.The electrochemical properties,lithiation mechanism,and structure evolution of composition-and morphology-dependent HEO anode are examined in detail.More importantly,the potential advantages of HEOs as electrode materials are evaluated from both theoretical and experimental aspects.Benefiting from the high oxygen vacancy concentration,narrow band gap,and structure durability induced by the multi-element synergy,HEO anode delivers desirable reversible capacity and reaction kinetics.In particular,Mg is evidenced to serve as a structural sustainer that significantly inhibits the volume expansion and retains the rock salt lattice.These new perspectives are expected to open a window of opportunity to compositionally/morphologi cally engineer high-performance HEO electrodes.
基金supported by the National Natural Science Foundation of China (No.52222311)the Shanghai RisingStar Program (20QA1406600)+2 种基金ChEM,SPST of Shanghai Tech University (#EM02161943)Shanghai Science and Technology Plan (21DZ2260400)Double First-Class Initiative Fund of Shanghai Tech University for supporting
文摘The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires a long processing time and an inert atmosphere.Here,a microwave-assisted ultrafast carbonization technique was developed that carbonizes natural wood in seconds without the need for an inert atmosphere,and the obtained aligned-porous carbonized wood provided an excellent electrochemical performance as an anode material for lithium-ion batteries.This ultrafast carbonization technique simultaneously produced ZnO nanoparticles during the carbonization process that were uniformly distributed on the alignedporous carbon.The hierarchical structure of carbonized wood functionalized with ZnO nanoparticles was used as a host for achieving high-performance lithium-sulfur batteries:the highly conductive carbonized wood framework with vertical channels provided good electron transport pathways,and the homogeneously dispersed ZnO nanoparticles effectively adsorbed lithium polysulfide and catalyzed its conversion reactions.In summary,a new method was developed to realize the ultrafast carbonization of biomass materials with decorated metal oxide nanoparticles.
基金the National Natural Science Foundation of China(Grant No.52072138,21571073,51772115)National Key Research and Development Program of China(Grant No.2018YFE0206900)Hubei Provincial Natural Science Foundation of China(Grant No.2019CFA002)。
文摘Among the alloying-type anodes,elemental Sb possesses the suitable yet safe plateau,simple lithiation pathway,small voltage polarization,high conductivity,and superior cycle stability.However,challenge is that its intrinsic capacity is rather low(660 mAh g^(-1)),<1/6 of silicon.Herein,we propose a seamless integration strategy by merging the voltage and capacity of phosphorus and antimony into a solid solution alloy.Interestingly,the enlistment of P is found greatly enlarge the capacity from 660 to 993 mAh g^(-1) for such Sb_(30)P_(30) solid solution,while maintaining a single and stable discharge plateau(~0.79 V)similar to elemental Sb.Various experimental characterizations including XPS,PDF,Raman,and EDS mapping reveal that in such a material the P and Sb atoms have interacted with each other to form a homogenous solid solution alloy,rather than a simple mixing of the two substances.Thus,the Sb_(30)P_(30) exhibits superior rate performances(807 mAh g^(-1) at 5000 mA g^(-1))and cyclability(821 mAh g^(-1) remained after 300 cycles).Furthermore,such Sb_(60-x)P_(x) alloys can even deliver 621 mAh g^(-1) at30℃,which can be served as the alternative anode materials for high-energy and low-temperature batteries.This unique seamless integration strategy based on solid solution chemistry can be easily leveraged to manipulate the capacity of other electrode materials at similar voltage.
基金supported by the National Key Research and Development Program of China(2019YFC1904500)National Natural Science Foundation of China(Nos.21801251,51502036,and 21875037)+2 种基金Young Top Talent of Fujian Young Eagle Program of Fujian Province,Educational Commis-sion of Fujian Province(2022G02022)Natural Science Foundation of Fuzhou City(2022-Y-004)Natural Science Foundation of Fujian Province(2023J02013).
文摘Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous batteries hinders their practical application.The solvent water freezes at low temperatures,and there is a reduction in ionic conductivity,whereas it evaporates rapidly at high temperatures,which causes increased side reactions.This review discusses recent progress in improving the performance of aqueous batteries,mainly with respect to electrolyte engineering and the associated strategies employed to achieve such improvements over a wide temperature domain.The review focuses on fi ve electrolyte engineer-ing(aqueous high-concentration electrolytes,organic electrolytes,quasi-solid/solid electrolytes,hybrid electrolytes,and eutectic electrolytes)and investigates the mechanisms involved in reducing the solidifi cation point and boiling point of the electrolyte and enhancing the extreme-temperature electrochemical performance.Finally,the prospect of further improving the wide temperature range performance of aqueous rechargeable batteries is presented.
基金supported by National Key Research and Development Program of China (No.2021YFF0500600)NSFC (22279120)Key R&D projects in Henan Province (221111240100)。
文摘Li-air batteries have attracted extensive attention because of their ultrahigh theoretical energy density. However, the potential safety hazard of flammable organic liquid electrolytes hinders their practical applications. Replacing liquid electrolytes with solidstate electrolytes(SSEs) is expected to fundamentally overcome the safety issues. In this work, we focus on the development and challenge of solid-state Li-air batteries(SSLABs). The rise of different types of SSEs, interfacial compatibility and verifiability in SSLABs are presented. The corresponding strategies and prospects of SSLABs are also proposed. In particular, combining machine learning method with experiment and in situ(or operando)techniques is imperative to accelerate the development of SSLABs.
基金the financial support of the National Natural Science Foundation of China(Nos.21875206,21403187)the Natural Science Foundation of Hebei Province(No.B2019203487)the open project in Key Lab Adv.Energy Mat.Chem.(Nankai University)。
文摘The development of novel organic electrode materials is of great significance for improving the reversible capacity and cycle stability of rechargeable batteries.Before practical application,it is essential to characterize the electrode materials to study their structures,redox mechanisms and electrochemical performances.In this review,the common characterization methods that have been adopted so far are summarized from two aspects:experimental characterization and theoretical calculation.The experimental characterization is introduced in detail from structural characterization,electrochemical characterization and electrode reaction chara cterization.The experimental purposes and working principles of various experimental characterization methods are briefly illustrated.As the auxilia ry means,theoretical calculation provides the theoretical basis for characterizing the electrochemical reaction mechanism of organic electrode materials.Through these characterizations,we will have a deep understanding about the material structures,electrochemical redox mechanisms,electrochemical properties and the relationships of structure-property.It is hoped that this review would help researchers to select the suitable characterization methods to analyze the structures and performances of organic electrode materials quickly and effectively.