The growing need for higher energy density in rechargeable batteries necessitates the exploration of cathode materials with enhanced specific energy for lithium-ion batteries.Due to their exceptional cost-effectivenes...The growing need for higher energy density in rechargeable batteries necessitates the exploration of cathode materials with enhanced specific energy for lithium-ion batteries.Due to their exceptional cost-effectiveness and specific capacity,lithium-rich manganese-based cathode materials(LRMs)obtain in-creasing attention in the pursuit of enhancing energy density and reducing costs.The implementation has faced obstacles in various applications due to substantial capacity and voltage degradation,insufficient safety performance,and restricted rate capability during cycling.These issues arise from the migration of transition metal,the release of oxygen,and structural transformation.In this review,we provide an integrated survey of the structure,lithium storage mechanism,challenges,and origins of LRMs,as well as recent advancements in various coating strategies.Particularly,the significance of optimizing the design of the cathode electrolyte interphase was emphasized to enhance electrode performance.Furthermore,future perspective was also addressed alongside in-situ measurements,advanced synthesis techniques,and the application of machine learning to overcome encountered challenges in LRMs.展开更多
The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based...The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.展开更多
The extensive use of diesel engines has led to significant emissions of pollutants,especially soot particles,which pose serious risks to both the environment and human health.At present,developing catalysts with low–...The extensive use of diesel engines has led to significant emissions of pollutants,especially soot particles,which pose serious risks to both the environment and human health.At present,developing catalysts with low–temperature activity,low cost,and high stability remains the core challenge in eliminating soot from diesel engine exhaust.This paper first reviews the mechanisms of soot catalytic oxidation.Based on these mechanisms,the current design directions for soot catalysts are summarized and discussed.On the one hand,the effects of modification methods such as doping,loading,and solid solution on the performance of manganese-based catalysts are reviewed from the perspective of intrinsic activity.On the other hand,the research progress on manganese-based catalysts with specific morphological structures for soot oxidation is explored.Following the identification of design strategies,the commonly used preparation methods to achieve these designs are also outlined.Finally,the paper highlights the challenges associated with manganese-based catalysts in soot catalysis and discusses future research and development directions.展开更多
Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-bas...Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-based layered oxide cathodes-a leading candidate for PIB systems-has been fundamentally constrained by irreversible phase transitions(PT)during the cycling process,manifesting as severe structural degradation and capacity fading.This review presents a transformative paradigm integrating machine learning(ML)with multiscale characterization to analyse the complex phase transition mechanisms in Mn-based cathodes.Through systematic ML-driven interrogation of structure-property relationships,we establish quantitative descriptors for phase stability and develop predictive models for transition dynamics.Furthermore,we highlight recent breakthroughs in cross-disciplinary approaches,enabling the rational design of PT-mitigated cathode architectures.By consolidating these insights into a unified knowledge framework,this work provides strategic guidelines for developing structurally robust Mn-based cathodes and outlines future research directions for next-generation PIB systems.展开更多
Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous ...Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.展开更多
Manganese(Mn)-based materials are considered as one of the most promising cathodes in zinc-ion batteries(ZIBs) for large-scale energy storage applications because of their multivalence, cost-effectiveness,natural avai...Manganese(Mn)-based materials are considered as one of the most promising cathodes in zinc-ion batteries(ZIBs) for large-scale energy storage applications because of their multivalence, cost-effectiveness,natural availability, low toxicity, satisfactory capacity, and high operating voltage. In this review, the research status and related interface engineering strategies of Mn-based oxide cathode electrode materials for ZIB in recent years are summarized. Specifically, the review will focus on three types of interface engineering strategies, including interface reconstruction via cathode, interface reconstruction electrolyte, and protection via artificial cathode-electrolyte interphase(CEI) layer, within the context of their evolution of interface layer and corresponding electrochemical performance. A series of experimental variables, such as crystal structure, electrochemical reaction mechanism, and the necessary connection for the formation and evolution of interface layer, will be carefully analyzed by combining various advanced characterization techniques and theoretical calculations. Finally, suggestions and strategies are provided for reasonably designing the cathode-electrolyte interface to realize the excellent performance of Mn-based oxide zinc-based batteries.展开更多
The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechar...The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechargeable ZIBs possess merits of high security,low cost,environmental friendliness,and competitive performance,and they are received a lot of attention.However,the development of suitable zinc ion intercalation-type cathode materials is still a big challenge,resulting in failing to meet the commercial needs of ZIBs.Both vanadium-based and manganese-based compounds are representative of the most advanced and most widely used rechargeable ZIBs electrodes.The valence state of vanadium is+2~+5,which can realize multi-electron transfer in the redox reaction and has a high specific capacity.Most of the manganese-based compounds have tunnel structure or three-dimensional space frame,with enough space to accommodate zinc ions.In order to understand the energy storage mechanism and electrochemical performance of these two materials,a specialized review focusing on state-of-the-art developments is needed.This review offers access for researchers to keep abreast of the research progress of cathode materials for ZIBs.The latest advanced researches in vanadium-based and manganese-based cathode materials applied in aqueous ZIBs are highlighted.This article will provide useful guidance for future studies on cathode materials and aqueous ZIBs.展开更多
With the development of industrialization,the emission of volatile organic compounds(VOCs)to atmosphere causes serious environmental problems and the treatment of VOCs needs to consume a lot of energy.Moreover,indoor ...With the development of industrialization,the emission of volatile organic compounds(VOCs)to atmosphere causes serious environmental problems and the treatment of VOCs needs to consume a lot of energy.Moreover,indoor VOCs are seriously harmful to human health.Thus,there is an urgent requirement for the development of indoor VOCs treatment technologies.Catalytic degradation of VOCs,as a low energy consumption,high efficiency,and easy to achieve manner,has been widely studied in related fields.As a kind of transition metal catalyst,manganese-based catalysts have attracted a lot of attention in the catalytic degradation of VOCs because of their unique advantages including high efficiency,low cost,and excellent stability.This paper reviews the state-of-the-art progress of manganese-based catalysts for VOCs catalytic degradation.We introduce the thermocatalytic,photocatalytic and photo-thermocatalytic degradation of VOCs on manganese-based catalysts in this paper.The optimization of manganese-based catalysts by means of structural design,decorating modification and defect engineering is discussed.展开更多
Aqueous zinc-ion batteries(AZIBs)are emerging as a promising option for next-generation energy storage due to their abundant resources,affordability,eco-friendliness,and high safety levels.Manganese-based cathode mate...Aqueous zinc-ion batteries(AZIBs)are emerging as a promising option for next-generation energy storage due to their abundant resources,affordability,eco-friendliness,and high safety levels.Manganese-based cathode materials,in particular,have garnered significant attention because of their high theoretical capacity and costeffectiveness.However,they still face substantial challenges related to rate performance and cycling stability.To address these issues,researchers have developed various strategies.This review focuses on the key advancements in manganesebased cathode materials for AZIBs in recent years.It begins with a detailed analysis of the energy storage mechanisms in manganese-based cathodes.Next,it introduces a variety of manganese-based oxides,highlighting their distinct crystal structures and morphologies.It also outlines optimization strategies,such as ion doping(both monovalent ions and multivalent ions),the preparation of Mn-based metal-organic frameworks(MOFs),carbon materials coatings,and electrolyte optimization.These strategies have significantly improved the electrochemical performance of manganesebased oxide cathodes.By systematically analyzing these advancements,it aims to provide guidance for the development of high-performance manganese-based cathodes.Finally,it discusses prospective research directions for manganesebased cathodes in AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising energy storage solution due to their eco-friendly aqueous electrolytes,high theoretical capacity of zinc anodes,and abundant global zinc reserves.Among the ...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising energy storage solution due to their eco-friendly aqueous electrolytes,high theoretical capacity of zinc anodes,and abundant global zinc reserves.Among the reported cathode materials,manganese-based cathodes are widely used in AZIBs due to their high theoretical capacity and low cost.However,practical applications of manganese-based cathodes face several challenges,including structural instability,low electrical conductivity,and slow diffusion kinetics.This review begins by exploring the crystalline structures of manganese-based compounds commonly used in AZIBs,systematically analyzing their reaction mechanisms.Furthermore,it examines the main challenges currently encountered by manganese-based compounds in AZIBs.Addressing these challenges,this review summarizes cor-responding optimization strategies,providing valuable references and insights for the development and application of manganese-based cathodes in AZIBs.展开更多
Low-cost Li-rich manganese-based cathodes are promising for rechargeable Li-ion batteries due to their high capacity and operating voltage.However,their large-scale application is hindered by surface structural change...Low-cost Li-rich manganese-based cathodes are promising for rechargeable Li-ion batteries due to their high capacity and operating voltage.However,their large-scale application is hindered by surface structural changes and oxygen release,which leads to irreversible capacity loss and poor cycling stability.This study investigates the use of solid electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)with NASICON structure as a coating material for Li-rich manganese-based cathode Li_(1.14)Ni_(0.27)Co_(0.03)Mn_(0.56)O_(2).LATP,known for its fast Li-ion conduction and excellent chemical stability,enhances Li-ion transport at the cathode–electrolyte interface and reduces the internal resistance of the cell.Our results show that LATPcoated Li-rich manganese cathodes have improved cycling performance and structural stability,highlighting the potential of LATP-coated Li-rich cathodes for high-performance Li-ion batteries.展开更多
The weak dielectric properties and the lack of magnetic loss of manganese-based absorbers are obstructed as the new generation of electromagnetic wave absorption(EMA)materials applying in microelectronic devices.Herei...The weak dielectric properties and the lack of magnetic loss of manganese-based absorbers are obstructed as the new generation of electromagnetic wave absorption(EMA)materials applying in microelectronic devices.Herein,the sulfuration and subsequent compounding strategies have been employed to enhance the EMA performance of multi-shell nanosphere-shaped Mn_(2)O_(3)materials.With the narrow bandgap,the as-obtained MnS possesses reinforced electrical conductivity,which is conducive to conductivity loss.More importantly,the presence of potential difference between different phases will form space charge region at the heterogeneous interface,thus favoring interfacial polarization.Additionally,the improvement of magnetic loss is attributed to the presence of Co_(3)O_(4)nanoparticles.Consequently,the composites present enhanced EMA performance than original Mn_(2)O_(3).Specifically,the minimum reflection loss of as-prepared composites is−51.4 dB at the thickness of 1.8 mm and the broad effective absorption bandwidth reaches 6.2 GHz at 1.9 mm.The low matching thickness and high absorption efficiency in this work can provide a convincing reference when designing distinguished manganese-based absorbers.展开更多
Lithium-rich manganese-based cathodes(R-LNCM)are potential candidates for next-generation Li^(+)bat-teries.However,their practical applications have impeded by the substantial voltage attenuation on cy-cling.The irrev...Lithium-rich manganese-based cathodes(R-LNCM)are potential candidates for next-generation Li^(+)bat-teries.However,their practical applications have impeded by the substantial voltage attenuation on cy-cling.The irreversible evolution of oxygen triggers transition-metal(TM)migration and structural re-arrangements,resulting in the voltage decay.Herein,a linkage-functionalized modification approach to tackle these challenges.The strategy involves the synchronous formation of an amorphous CuO coating,inner spinel structure,and oxygen vacancies on the surface of R-LNCM microspheres,effectively stabi-lizing the lattice oxygen evolution and suppressing structural distortion.Importantly,this three-in-one surface engineering approach is characterized by its environment-friendly attributes,cost-efficiency and seamless scalability.The corresponding cathode delivers a high specific capacity 298.2 mAh g^(-1)with ini-tial coulombic efficiency(ICE)95.18%at 0.1 C.The voltage decay and the capacity retention rate are 1.70 mV cycle^(-1)and 90.5%after 200 cycles at 1 C.The density functional theory shows that the diffusion energy barrier of Li^(+)in Li_(2)MnO_(3)can be reduced by introducing vacancy.Moreover,the introduction of spinel structure in R-LNCM material improves the stability and diffusion ability of R-LNCM.Therefore,the novel insight and method have a potential to make a significantly contribution to the commercialization of R-LNCM for high energy density batteries.展开更多
Li-ion batteries(LIBs)with excellent cycling stability and high-energy densities have already occupied the commercial rechargeable battery market.Unfortunately,the high cost and intrinsic insecurity induced by organic...Li-ion batteries(LIBs)with excellent cycling stability and high-energy densities have already occupied the commercial rechargeable battery market.Unfortunately,the high cost and intrinsic insecurity induced by organic electrolyte severely hinder their applications in large-scale energy storage.In contrast,aqueous Zn-ion batteries(ZIBs)are being developed as an ideal candidate because of their cheapness and high security.Benefiting from high operating voltage and acceptable specific capacity,recently,manganese-based oxides with different various crystal structures have been extensively studied as cathode materials for aqueous ZIBs.This review presents research progress of manganese-based cathodes in aqueous ZIBs,including various manganese-based oxides and their zinc storage mechanisms.In addition,we also discuss some optimization strategies that aim at improving the electrochemical performance of manganese-based cathodes,and the design of flexible aqueous ZIBs based on manganese-based cathodes(MZIBs).Finally,this review summarizes some valuable research directions,which will promote the further development of aqueous MZIBs.展开更多
Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but...Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but also inhibits the structural strain during cycling processes.Herein,we report the hierarchical flower-like pure spinel manganese-based oxide nanosheets synthesized via a template-orientated strategy.The oriented template is fabricated by decomposition of carbonate obtained from"bubble reaction",via an alcoholassisted hydrothermal process.The resultant spinel manganese-based oxide nanosheets simultaneously possess excellent rate capability and cycling stability.The high-voltage LiNi0.5Mn1.5O4(LNMO-HF)has a uniform phase distribution without the common impurity phase LixNi1-xO2 and NixO.Besides,the LNMO-HF delivers high discharge capacity of142.6 mA h g-with specific energy density of 660.7 W h kg 1 at 1 C under 55℃.More importantly,the template-orientated strategy can be extended to the synthesis of LiMn2 O4(LMO),which can achieve 88.12%capacity retention after 1000 cycles.展开更多
Li-rich manganese-based cathode materials(LR) are considered as excellent cathode materials for a new generation of lithium-ion batteries causes their outstanding electrochemical performance, friendly price, and envir...Li-rich manganese-based cathode materials(LR) are considered as excellent cathode materials for a new generation of lithium-ion batteries causes their outstanding electrochemical performance, friendly price, and environmental friendliness. But defects such as rapid voltage decay and loss of lattice oxygen limit their applications. The electrochemical performance of LR has to be improved by means of modification. The previous single modification methods like element doping, surface coating, structure design, etc. can only optimize the electrochemical performance of LR from one aspect. Recently, multiple modifications,which can combine the advantages of multiple modifications, have been favored by researchers. Here, we comprehensively review the recent progress of multiple modification of LR based on the combination of different modification means. The review and summary of the multiple modification of LR will play a guiding role in its development in the future.展开更多
Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through s...Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through synergistic anionic and cationic redox reactions.However,these materials face challenges including oxygen release-induced structural degradation and consequent capacity fading.To address these issues,strategies such as surface modification and bulk phase engineering have been explored.In this study,we developed a facile and cost-effective quenching approach that simultaneously modifies both surface and bulk characteristics.Multi-scale characterization and computational analysis reveal that rapid cooling partially preserves the high-temperature disordered phase in the bulk structure,thereby enhancing the structural stability.Concurrently,Li^(+)/H^(+)exchange at the surface forms a robust rock-salt/spinel passivation layer,effectively suppressing oxygen evolution and mitigating interfacial side reactions.This dual modification strategy demonstrates a synergistic stabilization effect.The enhanced oxygen redox activity coexists with the improved structural integrity,leading to superior electrochemical performance.The optimized cathode delivers an initial discharge capacity approaching 307.14 mAh/g at 0.1 C and remarkable cycling stability with 94.12%capacity retention after 200 cycles at 1 C.This study presents a straightforward and economical strategy for concurrent surface–bulk modification,offering valuable insights for designing high-capacity LRM cathodes with extended cycle life.展开更多
As the primary suppliers of cyclable sodium ions,O3-type layer-structured manganese-based oxides are recognized as highly competitive cathode candidates for sodium-ion batteries.To advance the development of high-ener...As the primary suppliers of cyclable sodium ions,O3-type layer-structured manganese-based oxides are recognized as highly competitive cathode candidates for sodium-ion batteries.To advance the development of high-energy sodium-ion batteries,it is crucial to explore cathode materials operating at high voltages while maintaining a stable cycling behavior.The orbital and electronic structure of the octahedral center metal element plays a crucial role in maintaining the octahedra structural integrity and improving Na^(+)ion diffusion by introducing heterogeneous chemical bonding.Inspired by the abundant configuration of extra nuclear electrons and large ion radius,we employed trace amounts of tungsten in this study.The obtained cathode material can promote the reversibility of oxygen redox reactions in the high-voltage region and inhibit the loss of lattice oxygen.Additionally,the formation of a Na_(2)WO_(4) coating on the material surface can improve the interfacial stability and interface ions diffusion.It demonstrates an initial Coulombic efficiency(ICE)of 94.6%along with 168.5 mA h g^(-1 )discharge capacity within the voltage range of 1.9-4.35 V.These findings contribute to the advancement of high-energy sodium-ion batteries by providing insights into the benefits of tungsten doping and Na_(2)WO_(4) coating on cathode materials.展开更多
Manganese-based oxide electrode materials suffer from severe Jahn-Teller(J-T)distortion,leading to severe cycle instability in sodium ion storage.However,it is difficult to adjust the electron at d orbitals exactly to...Manganese-based oxide electrode materials suffer from severe Jahn-Teller(J-T)distortion,leading to severe cycle instability in sodium ion storage.However,it is difficult to adjust the electron at d orbitals exactly to a low spin state to eliminate orbital degeneracy and suppress J-T distortion fundamentally.This article constructed concentration-controllable Mn/O coupled vacancy and amorphous network in Mn_(3)O_(4) and coated it with nitrogen-doped carbon aerogel(Mn_(3-x)O_(4-y)@NCA).The existence of Mn/O vacancies has been confirmed by scanning transmission electron microscopy(STEM)and positron annihilation lifetime spectroscopy(PALS).Atomic absorption spectroscopy(AAS)and X-ray photoelectron spectroscopy(XPS)determine the most optimal ratio of Mn/O vacancies for sodium ion storage is 1:2.Density functional theory(DFT)calculations prove that Mn/O coupled vacancies with the ratio of 1:2could exactly induce a low spin states and a d~4 electron configuration of Mn,suppressing the J-T distortion successfully.The abundant amorphous regions can shorten the transport distance of sodium ions,increase the electrochemically active sites and improve the pseudocapacitance response.From the synergetic effect of Mn/O coupled vacancies and amorphous regions,Mn_(3-x)O_(4-y)@NCA exhibits an energy density of 37.5 W h kg^(-1)and an ultra-high power density of 563 W kg^(-1)in an asymmetric supercapacitor.In sodium-ion batteries,it demonstrates high reversible capacity and exceptional cycling stability.This research presents a new method to improve the Na^(+)storage performance in manganese-based oxide,which is expected to be generalized to other structural distortion.展开更多
As the cyclable sodium ions'primary suppliers,O3-type layer-structured manganese-based oxides are recognized as one of the most competitive cathode candidates for sodium-ion batteries.Suffering from complex struct...As the cyclable sodium ions'primary suppliers,O3-type layer-structured manganese-based oxides are recognized as one of the most competitive cathode candidates for sodium-ion batteries.Suffering from complex structural transformations and transition metal migration during the sodium intercalation/deintercalation process,particularly at high voltage,the energy density and lifespan cannot satisfy the increasing demand.The orbital and electronic structure of the octahedral center metal element plays an important role in maintaining the octahedral structural integrity and improving the Na+diffusivity by the introduced heterogeneous[Me-O](Me:transition metals)chemical bonding.Herein,inspired by the 4f and 5d orbital bonding possibility from the abundant configuration of extranuclear electrons and large ion radius,O3-type Na[La_(0.01)Ni_(0.3)Mn_(0.54)Cu_(0.1)Ti_(0.05)]O_(2) was synthesized with a nearly single crystal structure.Based on the experimental and computational results,the introduced heterogeneous[La-O]chemical bond with larger bond strength can not only ensure the stability of the lattice oxygen framework and the reversibility of oxygen redox but also optimize the oxygen local electronic structure resulting from La 5d and O 2p orbital mixing due to O 2p→La 5d charge transfer.It delivers an optimal electrochemical performance with a high energy density and cycling lifespan.展开更多
基金the support from the National Natural Science Foun-dation of China(Grant No.U21A20311)the Distinguished Scientist Fellowship Program(DSFP)at King Saud University,Riyadh,Saudi Arabia.
文摘The growing need for higher energy density in rechargeable batteries necessitates the exploration of cathode materials with enhanced specific energy for lithium-ion batteries.Due to their exceptional cost-effectiveness and specific capacity,lithium-rich manganese-based cathode materials(LRMs)obtain in-creasing attention in the pursuit of enhancing energy density and reducing costs.The implementation has faced obstacles in various applications due to substantial capacity and voltage degradation,insufficient safety performance,and restricted rate capability during cycling.These issues arise from the migration of transition metal,the release of oxygen,and structural transformation.In this review,we provide an integrated survey of the structure,lithium storage mechanism,challenges,and origins of LRMs,as well as recent advancements in various coating strategies.Particularly,the significance of optimizing the design of the cathode electrolyte interphase was emphasized to enhance electrode performance.Furthermore,future perspective was also addressed alongside in-situ measurements,advanced synthesis techniques,and the application of machine learning to overcome encountered challenges in LRMs.
基金National Natural Science Foundation of China,Grant/Award Numbers:22179008,21875022Yibin“Jie Bang Gua Shuai”,Grant/Award Number:2022JB004+2 种基金Beijing Nova Program,Grant/Award Number:20230484241Postdoctoral Fellowship Program of CPSF,Grant/Award Number:GZB20230931Special Support of Chongqing Postdoctoral Research Project,Grant/Award Number:2023CQBSHTB2041。
文摘The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.
基金sponsored by the National Natural Science Foundation of China(Grant 22406050)the Top-Notch Personnel Fund of Henan Agricultural University(Grant 30501029)+2 种基金the Natural Science Foundation of Henan Province(Grant 232300420293)the Science and Technology Project of China Tobacco Shaanxi Industrial Co.,Ltd.(Grant BA000-ZB24010)the Postgraduate Education Reform and Quality Improvement Project of Henan Province(Grant YJS2024JD17).
文摘The extensive use of diesel engines has led to significant emissions of pollutants,especially soot particles,which pose serious risks to both the environment and human health.At present,developing catalysts with low–temperature activity,low cost,and high stability remains the core challenge in eliminating soot from diesel engine exhaust.This paper first reviews the mechanisms of soot catalytic oxidation.Based on these mechanisms,the current design directions for soot catalysts are summarized and discussed.On the one hand,the effects of modification methods such as doping,loading,and solid solution on the performance of manganese-based catalysts are reviewed from the perspective of intrinsic activity.On the other hand,the research progress on manganese-based catalysts with specific morphological structures for soot oxidation is explored.Following the identification of design strategies,the commonly used preparation methods to achieve these designs are also outlined.Finally,the paper highlights the challenges associated with manganese-based catalysts in soot catalysis and discusses future research and development directions.
基金financially supported by the National Natural Science Foundation of China(U20A20247)the National Key Research and Development Program of the Ministry of Science and Technology(2022YFA1402504)+1 种基金Guangdong Provincial Key Laboratory of Materials and Technologies for Energy Conversion(MATEC2023KF002)Guangdong Science and Technology Department(STKJ2021016)。
文摘Potassium-ion batteries(PIBs)were recognized for their natural abunda nce,high theoretical output voltage,and the availability of commercialized graphite anodes.However,the development of highperformance manganese-based layered oxide cathodes-a leading candidate for PIB systems-has been fundamentally constrained by irreversible phase transitions(PT)during the cycling process,manifesting as severe structural degradation and capacity fading.This review presents a transformative paradigm integrating machine learning(ML)with multiscale characterization to analyse the complex phase transition mechanisms in Mn-based cathodes.Through systematic ML-driven interrogation of structure-property relationships,we establish quantitative descriptors for phase stability and develop predictive models for transition dynamics.Furthermore,we highlight recent breakthroughs in cross-disciplinary approaches,enabling the rational design of PT-mitigated cathode architectures.By consolidating these insights into a unified knowledge framework,this work provides strategic guidelines for developing structurally robust Mn-based cathodes and outlines future research directions for next-generation PIB systems.
基金This work was supported by the Fundamental Research Funds for the Central Universities(DUT20LAB123 and DUT20LAB307)the Natural Science Foundation of Jiangsu Province(BK20191167).
文摘Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.
基金financial support from the National Natural Science Foundation of China (No. 21676036)the Natural Science Foundation of Chongqing (No. CSTB2023NSCQMSX0580)。
文摘Manganese(Mn)-based materials are considered as one of the most promising cathodes in zinc-ion batteries(ZIBs) for large-scale energy storage applications because of their multivalence, cost-effectiveness,natural availability, low toxicity, satisfactory capacity, and high operating voltage. In this review, the research status and related interface engineering strategies of Mn-based oxide cathode electrode materials for ZIB in recent years are summarized. Specifically, the review will focus on three types of interface engineering strategies, including interface reconstruction via cathode, interface reconstruction electrolyte, and protection via artificial cathode-electrolyte interphase(CEI) layer, within the context of their evolution of interface layer and corresponding electrochemical performance. A series of experimental variables, such as crystal structure, electrochemical reaction mechanism, and the necessary connection for the formation and evolution of interface layer, will be carefully analyzed by combining various advanced characterization techniques and theoretical calculations. Finally, suggestions and strategies are provided for reasonably designing the cathode-electrolyte interface to realize the excellent performance of Mn-based oxide zinc-based batteries.
基金financially supported by the National Natural Science Foundation of China(No.51872090,51772097)the Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433,E2017209079)the financial support from Hunan Provincial Science and Technology Plan Project of China(No.2016TP1007,2017TP1001,and 2018RS3009)。
文摘The growing demand for energy storage has inspired researchers’exploration of advanced batteries.Aqueous zinc ion batteries(ZIBs)are promising secondary chemical battery system that can be selected and pursued.Rechargeable ZIBs possess merits of high security,low cost,environmental friendliness,and competitive performance,and they are received a lot of attention.However,the development of suitable zinc ion intercalation-type cathode materials is still a big challenge,resulting in failing to meet the commercial needs of ZIBs.Both vanadium-based and manganese-based compounds are representative of the most advanced and most widely used rechargeable ZIBs electrodes.The valence state of vanadium is+2~+5,which can realize multi-electron transfer in the redox reaction and has a high specific capacity.Most of the manganese-based compounds have tunnel structure or three-dimensional space frame,with enough space to accommodate zinc ions.In order to understand the energy storage mechanism and electrochemical performance of these two materials,a specialized review focusing on state-of-the-art developments is needed.This review offers access for researchers to keep abreast of the research progress of cathode materials for ZIBs.The latest advanced researches in vanadium-based and manganese-based cathode materials applied in aqueous ZIBs are highlighted.This article will provide useful guidance for future studies on cathode materials and aqueous ZIBs.
基金financially supported by the National Natural Science Foundation of China(No.22071173)the Natural Science Foundation of Tianjin City(No.20JCJQJC00050)。
文摘With the development of industrialization,the emission of volatile organic compounds(VOCs)to atmosphere causes serious environmental problems and the treatment of VOCs needs to consume a lot of energy.Moreover,indoor VOCs are seriously harmful to human health.Thus,there is an urgent requirement for the development of indoor VOCs treatment technologies.Catalytic degradation of VOCs,as a low energy consumption,high efficiency,and easy to achieve manner,has been widely studied in related fields.As a kind of transition metal catalyst,manganese-based catalysts have attracted a lot of attention in the catalytic degradation of VOCs because of their unique advantages including high efficiency,low cost,and excellent stability.This paper reviews the state-of-the-art progress of manganese-based catalysts for VOCs catalytic degradation.We introduce the thermocatalytic,photocatalytic and photo-thermocatalytic degradation of VOCs on manganese-based catalysts in this paper.The optimization of manganese-based catalysts by means of structural design,decorating modification and defect engineering is discussed.
基金supported by the National Natural Science Foundations of China(Grant Nos.21406139 and 52172095).
文摘Aqueous zinc-ion batteries(AZIBs)are emerging as a promising option for next-generation energy storage due to their abundant resources,affordability,eco-friendliness,and high safety levels.Manganese-based cathode materials,in particular,have garnered significant attention because of their high theoretical capacity and costeffectiveness.However,they still face substantial challenges related to rate performance and cycling stability.To address these issues,researchers have developed various strategies.This review focuses on the key advancements in manganesebased cathode materials for AZIBs in recent years.It begins with a detailed analysis of the energy storage mechanisms in manganese-based cathodes.Next,it introduces a variety of manganese-based oxides,highlighting their distinct crystal structures and morphologies.It also outlines optimization strategies,such as ion doping(both monovalent ions and multivalent ions),the preparation of Mn-based metal-organic frameworks(MOFs),carbon materials coatings,and electrolyte optimization.These strategies have significantly improved the electrochemical performance of manganesebased oxide cathodes.By systematically analyzing these advancements,it aims to provide guidance for the development of high-performance manganese-based cathodes.Finally,it discusses prospective research directions for manganesebased cathodes in AZIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.52263016 and 22265007)the Natural Science Foundation of Guangxi Province(Nos.2022GXNSFAA035597,2023GXNSFAA026162,and AB23075171).
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising energy storage solution due to their eco-friendly aqueous electrolytes,high theoretical capacity of zinc anodes,and abundant global zinc reserves.Among the reported cathode materials,manganese-based cathodes are widely used in AZIBs due to their high theoretical capacity and low cost.However,practical applications of manganese-based cathodes face several challenges,including structural instability,low electrical conductivity,and slow diffusion kinetics.This review begins by exploring the crystalline structures of manganese-based compounds commonly used in AZIBs,systematically analyzing their reaction mechanisms.Furthermore,it examines the main challenges currently encountered by manganese-based compounds in AZIBs.Addressing these challenges,this review summarizes cor-responding optimization strategies,providing valuable references and insights for the development and application of manganese-based cathodes in AZIBs.
基金financially supported by the Lowcost Cathode Material Project(TC220H06P)。
文摘Low-cost Li-rich manganese-based cathodes are promising for rechargeable Li-ion batteries due to their high capacity and operating voltage.However,their large-scale application is hindered by surface structural changes and oxygen release,which leads to irreversible capacity loss and poor cycling stability.This study investigates the use of solid electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)with NASICON structure as a coating material for Li-rich manganese-based cathode Li_(1.14)Ni_(0.27)Co_(0.03)Mn_(0.56)O_(2).LATP,known for its fast Li-ion conduction and excellent chemical stability,enhances Li-ion transport at the cathode–electrolyte interface and reduces the internal resistance of the cell.Our results show that LATPcoated Li-rich manganese cathodes have improved cycling performance and structural stability,highlighting the potential of LATP-coated Li-rich cathodes for high-performance Li-ion batteries.
基金supported by the Natural Science Foundation of Shandong Province(No.ZR2019YQ24)Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)the Qingchuang Talents Induction Program of Shandong Higher Education Institution(Research and Innovation Team of Structural-Functional Polymer Composites).
文摘The weak dielectric properties and the lack of magnetic loss of manganese-based absorbers are obstructed as the new generation of electromagnetic wave absorption(EMA)materials applying in microelectronic devices.Herein,the sulfuration and subsequent compounding strategies have been employed to enhance the EMA performance of multi-shell nanosphere-shaped Mn_(2)O_(3)materials.With the narrow bandgap,the as-obtained MnS possesses reinforced electrical conductivity,which is conducive to conductivity loss.More importantly,the presence of potential difference between different phases will form space charge region at the heterogeneous interface,thus favoring interfacial polarization.Additionally,the improvement of magnetic loss is attributed to the presence of Co_(3)O_(4)nanoparticles.Consequently,the composites present enhanced EMA performance than original Mn_(2)O_(3).Specifically,the minimum reflection loss of as-prepared composites is−51.4 dB at the thickness of 1.8 mm and the broad effective absorption bandwidth reaches 6.2 GHz at 1.9 mm.The low matching thickness and high absorption efficiency in this work can provide a convincing reference when designing distinguished manganese-based absorbers.
基金financially supported by the National Key Re-search and Development Program of China(No.2021YFB2400401).
文摘Lithium-rich manganese-based cathodes(R-LNCM)are potential candidates for next-generation Li^(+)bat-teries.However,their practical applications have impeded by the substantial voltage attenuation on cy-cling.The irreversible evolution of oxygen triggers transition-metal(TM)migration and structural re-arrangements,resulting in the voltage decay.Herein,a linkage-functionalized modification approach to tackle these challenges.The strategy involves the synchronous formation of an amorphous CuO coating,inner spinel structure,and oxygen vacancies on the surface of R-LNCM microspheres,effectively stabi-lizing the lattice oxygen evolution and suppressing structural distortion.Importantly,this three-in-one surface engineering approach is characterized by its environment-friendly attributes,cost-efficiency and seamless scalability.The corresponding cathode delivers a high specific capacity 298.2 mAh g^(-1)with ini-tial coulombic efficiency(ICE)95.18%at 0.1 C.The voltage decay and the capacity retention rate are 1.70 mV cycle^(-1)and 90.5%after 200 cycles at 1 C.The density functional theory shows that the diffusion energy barrier of Li^(+)in Li_(2)MnO_(3)can be reduced by introducing vacancy.Moreover,the introduction of spinel structure in R-LNCM material improves the stability and diffusion ability of R-LNCM.Therefore,the novel insight and method have a potential to make a significantly contribution to the commercialization of R-LNCM for high energy density batteries.
基金This work was financially supported by This work was financially supported by the National Natural Science Foundation of China(21725103 and 51631004)National Key R&D Program of China(2016YFB0100103,2017YFA0206704)+2 种基金People's Government of Jilin Province Science and Technology Development Plan Funding Project(20180101203JC)Changchun Science and Technology Development Plan Funding Project(18DY012,19SS010)the Program for the JLU Science and Technology Innovative Research Team(2017TD-09).
文摘Li-ion batteries(LIBs)with excellent cycling stability and high-energy densities have already occupied the commercial rechargeable battery market.Unfortunately,the high cost and intrinsic insecurity induced by organic electrolyte severely hinder their applications in large-scale energy storage.In contrast,aqueous Zn-ion batteries(ZIBs)are being developed as an ideal candidate because of their cheapness and high security.Benefiting from high operating voltage and acceptable specific capacity,recently,manganese-based oxides with different various crystal structures have been extensively studied as cathode materials for aqueous ZIBs.This review presents research progress of manganese-based cathodes in aqueous ZIBs,including various manganese-based oxides and their zinc storage mechanisms.In addition,we also discuss some optimization strategies that aim at improving the electrochemical performance of manganese-based cathodes,and the design of flexible aqueous ZIBs based on manganese-based cathodes(MZIBs).Finally,this review summarizes some valuable research directions,which will promote the further development of aqueous MZIBs.
基金financially supported by the National Natural Science Foundation of China(21371023)
文摘Hierarchical flower-structured two-dimensional(2 D)nanosheet is favorable for electrochemical reactions.The unique structure not only exposes the maximized active sites and shortens ion/electron diffusion channels,but also inhibits the structural strain during cycling processes.Herein,we report the hierarchical flower-like pure spinel manganese-based oxide nanosheets synthesized via a template-orientated strategy.The oriented template is fabricated by decomposition of carbonate obtained from"bubble reaction",via an alcoholassisted hydrothermal process.The resultant spinel manganese-based oxide nanosheets simultaneously possess excellent rate capability and cycling stability.The high-voltage LiNi0.5Mn1.5O4(LNMO-HF)has a uniform phase distribution without the common impurity phase LixNi1-xO2 and NixO.Besides,the LNMO-HF delivers high discharge capacity of142.6 mA h g-with specific energy density of 660.7 W h kg 1 at 1 C under 55℃.More importantly,the template-orientated strategy can be extended to the synthesis of LiMn2 O4(LMO),which can achieve 88.12%capacity retention after 1000 cycles.
基金supported by the Natural Science Foundation of Hunan Province(Nos.2021JJ30823 and 2020JJ2048)National Natural Science Foundation of China(No.51974368)。
文摘Li-rich manganese-based cathode materials(LR) are considered as excellent cathode materials for a new generation of lithium-ion batteries causes their outstanding electrochemical performance, friendly price, and environmental friendliness. But defects such as rapid voltage decay and loss of lattice oxygen limit their applications. The electrochemical performance of LR has to be improved by means of modification. The previous single modification methods like element doping, surface coating, structure design, etc. can only optimize the electrochemical performance of LR from one aspect. Recently, multiple modifications,which can combine the advantages of multiple modifications, have been favored by researchers. Here, we comprehensively review the recent progress of multiple modification of LR based on the combination of different modification means. The review and summary of the multiple modification of LR will play a guiding role in its development in the future.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB2502200)the National Natural Science Foundation of China(Grant Nos.52325207,22239003,and 22393904).
文摘Lithium-rich manganese-based cathodes(LRMs)have garnered significant attention as promising candidates for highenergy-density batteries due to their exceptional specific capacity exceeding 300 mAh/g,achieved through synergistic anionic and cationic redox reactions.However,these materials face challenges including oxygen release-induced structural degradation and consequent capacity fading.To address these issues,strategies such as surface modification and bulk phase engineering have been explored.In this study,we developed a facile and cost-effective quenching approach that simultaneously modifies both surface and bulk characteristics.Multi-scale characterization and computational analysis reveal that rapid cooling partially preserves the high-temperature disordered phase in the bulk structure,thereby enhancing the structural stability.Concurrently,Li^(+)/H^(+)exchange at the surface forms a robust rock-salt/spinel passivation layer,effectively suppressing oxygen evolution and mitigating interfacial side reactions.This dual modification strategy demonstrates a synergistic stabilization effect.The enhanced oxygen redox activity coexists with the improved structural integrity,leading to superior electrochemical performance.The optimized cathode delivers an initial discharge capacity approaching 307.14 mAh/g at 0.1 C and remarkable cycling stability with 94.12%capacity retention after 200 cycles at 1 C.This study presents a straightforward and economical strategy for concurrent surface–bulk modification,offering valuable insights for designing high-capacity LRM cathodes with extended cycle life.
基金supported by the National Natural Science Foundation of China(Grant No.52272194)LiaoNing Revitalization Talents Program(Grant No.XLYC2007155)。
文摘As the primary suppliers of cyclable sodium ions,O3-type layer-structured manganese-based oxides are recognized as highly competitive cathode candidates for sodium-ion batteries.To advance the development of high-energy sodium-ion batteries,it is crucial to explore cathode materials operating at high voltages while maintaining a stable cycling behavior.The orbital and electronic structure of the octahedral center metal element plays a crucial role in maintaining the octahedra structural integrity and improving Na^(+)ion diffusion by introducing heterogeneous chemical bonding.Inspired by the abundant configuration of extra nuclear electrons and large ion radius,we employed trace amounts of tungsten in this study.The obtained cathode material can promote the reversibility of oxygen redox reactions in the high-voltage region and inhibit the loss of lattice oxygen.Additionally,the formation of a Na_(2)WO_(4) coating on the material surface can improve the interfacial stability and interface ions diffusion.It demonstrates an initial Coulombic efficiency(ICE)of 94.6%along with 168.5 mA h g^(-1 )discharge capacity within the voltage range of 1.9-4.35 V.These findings contribute to the advancement of high-energy sodium-ion batteries by providing insights into the benefits of tungsten doping and Na_(2)WO_(4) coating on cathode materials.
基金supported by the National Natural Science Foundation of China (22278231,22005165 and 22376110)the Natural Science Foundation Project of Shandong Province (ZR2022MB092 and ZR2023ME098)the Taishan Scholar Program (ts201712030)。
文摘Manganese-based oxide electrode materials suffer from severe Jahn-Teller(J-T)distortion,leading to severe cycle instability in sodium ion storage.However,it is difficult to adjust the electron at d orbitals exactly to a low spin state to eliminate orbital degeneracy and suppress J-T distortion fundamentally.This article constructed concentration-controllable Mn/O coupled vacancy and amorphous network in Mn_(3)O_(4) and coated it with nitrogen-doped carbon aerogel(Mn_(3-x)O_(4-y)@NCA).The existence of Mn/O vacancies has been confirmed by scanning transmission electron microscopy(STEM)and positron annihilation lifetime spectroscopy(PALS).Atomic absorption spectroscopy(AAS)and X-ray photoelectron spectroscopy(XPS)determine the most optimal ratio of Mn/O vacancies for sodium ion storage is 1:2.Density functional theory(DFT)calculations prove that Mn/O coupled vacancies with the ratio of 1:2could exactly induce a low spin states and a d~4 electron configuration of Mn,suppressing the J-T distortion successfully.The abundant amorphous regions can shorten the transport distance of sodium ions,increase the electrochemically active sites and improve the pseudocapacitance response.From the synergetic effect of Mn/O coupled vacancies and amorphous regions,Mn_(3-x)O_(4-y)@NCA exhibits an energy density of 37.5 W h kg^(-1)and an ultra-high power density of 563 W kg^(-1)in an asymmetric supercapacitor.In sodium-ion batteries,it demonstrates high reversible capacity and exceptional cycling stability.This research presents a new method to improve the Na^(+)storage performance in manganese-based oxide,which is expected to be generalized to other structural distortion.
基金National Natural Science Foundation of China,Grant/Award Number:52272194Liaoning Province Revitalization Talent Program,Grant/Award Number:XLYC2007155.
文摘As the cyclable sodium ions'primary suppliers,O3-type layer-structured manganese-based oxides are recognized as one of the most competitive cathode candidates for sodium-ion batteries.Suffering from complex structural transformations and transition metal migration during the sodium intercalation/deintercalation process,particularly at high voltage,the energy density and lifespan cannot satisfy the increasing demand.The orbital and electronic structure of the octahedral center metal element plays an important role in maintaining the octahedral structural integrity and improving the Na+diffusivity by the introduced heterogeneous[Me-O](Me:transition metals)chemical bonding.Herein,inspired by the 4f and 5d orbital bonding possibility from the abundant configuration of extranuclear electrons and large ion radius,O3-type Na[La_(0.01)Ni_(0.3)Mn_(0.54)Cu_(0.1)Ti_(0.05)]O_(2) was synthesized with a nearly single crystal structure.Based on the experimental and computational results,the introduced heterogeneous[La-O]chemical bond with larger bond strength can not only ensure the stability of the lattice oxygen framework and the reversibility of oxygen redox but also optimize the oxygen local electronic structure resulting from La 5d and O 2p orbital mixing due to O 2p→La 5d charge transfer.It delivers an optimal electrochemical performance with a high energy density and cycling lifespan.
