Aqueous zinc-ion batteries(ZIBs)have got wide attention with the increasing demands for energy resource recently.It has a number of merits compared with lithium-ion batteries,such as enhanced safety,low cost and envir...Aqueous zinc-ion batteries(ZIBs)have got wide attention with the increasing demands for energy resource recently.It has a number of merits compared with lithium-ion batteries,such as enhanced safety,low cost and environmental friendliness.Vanadium-based materials have been developed to serve as the cathodes of ZIBs for many years.But there are also some challenges to construct high performance ZIBs in the future.Herein,we reviewed the research progress of vanadium-based cathodes and discussed the energy storage mechanisms in ZIBs.In addition,we summarized the major challenges faced by vanadium-based cathodes and the corresponding ways to improve electrochemical performance of ZIBs.Finally,some excellent vanadium-based cathodes are summarized to pave the way for future research in ZIBs.展开更多
As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries(AZIBs) have attracted more and more attenti...As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries(AZIBs) have attracted more and more attention. Vanadium-based compounds are also supposed as the potential candidate cathode materials for AZIBs due to their wide variety of phases, variable crystal structures and high theoretical capacity. In this review, the recent progress in the development of vanadium-based materials was summarized,and the relationship between the crystal structure types of active materials and Zn-ion transport mechanism was highlighted. During the charge-discharge process, the different electrostatic repulsion between the cations of vanadium-based compounds with different crystal structures and Zn^(2+)results in a variety of the Zn-ion storage mechanisms, which can be significant guidance for designing the advanced batteryelectrode materials for AZIBs. Furthermore, other factors associated with the storage mechanisms, such as electrolyte components and electrode morphology, are discussed. Finally, the strategies to improve the electrical conductivity, inhibit the dissolution and stabilize the crystal structure of vanadium-based compounds are proposed and the future prospects for developing high-energy-density AZIBs are presented.展开更多
Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage...Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.展开更多
Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available...Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available cathode materials,vanadium-based sodium phosphate cathodes are particularly notable for their high operating voltage,excellent thermal stability,and superior cycling performance.However,these materials face significant challenges,including sluggish reaction kinetics,the toxicity of vanadium,and poor electronic conductivity.To overcome these limitations and enhance electrochemical performance,various strategies have been explored.These include morphology regulation via diverse synthesis routes and electronic structure optimization through metal doping,which effectively improve the diffusion of Na+and electrons in vanadium-based phosphate cathodes.This review provides a comprehensive overview of the challenges associated with V-based polyanion cathodes and examines the role of morphology and electronic structure design in enhancing performance.Key vanadium-based phosphate frameworks,such as orthophosphates(Na_(3)V_(2)(PO_(4))_(3)),pyrophosphates(NaVP_(2)O_(7),Na_(2)(VO)P_(2)O_(7),Na_(7)V_(3)(P_(2)O_(7))_(4)),and mixed phosphates(Na_(7)V_(4)(P_(2)O_(7))_(4)PO_(4)),are discussed in detail,highlighting recent advances and insights into their structure-property relationships.The design of cathode material morphology offers an effective approach to optimizing material structures,compositions,porosity,and ion/electron diffusion pathways.Simultaneously,electronic structure tuning through element doping allows for the regulation of band structures,electron distribution,diffusion barriers,and the intrinsic conductivity of phosphate compounds.Addressing the challenges associated with vanadium-based sodium phosphate cathode materials,this study proposes feasible solutions and outlines future research directions toward advancement of high-performance vanadium-based polyanion cathodes.展开更多
Lithium manganese silicate(Li-Mn-Si-O)cathodes are key components of lithium-ion batteries,and their physical and mechanical properties are strongly influenced by their underlying crystal structures.In this study,a ra...Lithium manganese silicate(Li-Mn-Si-O)cathodes are key components of lithium-ion batteries,and their physical and mechanical properties are strongly influenced by their underlying crystal structures.In this study,a range of machine learning(ML)algorithms were developed and compared to predict the crystal systems of Li-Mn-Si-O cathode materials using density functional theory(DFT)data obtained from the Materials Project database.The dataset comprised 211 compositions characterized by key descriptors,including formation energy,energy above the hull,bandgap,atomic site number,density,and unit cell volume.These features were utilized to classify the materials into monoclinic(0)and triclinic(1)crystal systems.A comprehensive comparison of various classification algorithms including Decision Tree,Random Forest,XGBoost,Support VectorMachine,k-Nearest Neighbor,Stochastic Gradient Descent,Gaussian Naive Bayes,Gaussian Process,and Artificial Neural Network(ANN)was conducted.Among these,the optimized ANN architecture(6–14-14-14-1)exhibited the highest predictive performance,achieving an accuracy of 95.3%,aMatthews correlation coefficient(MCC)of 0.894,and an F-score of 0.963,demonstrating excellent consistency with DFT-predicted crystal structures.Meanwhile,RandomForest and Gaussian Processmodels also exhibited reliable and consistent predictive capability,indicating their potential as complementary approaches,particularly when data are limited or computational efficiency is required.This comparative framework provides valuable insights into model selection for crystal system classification in complex cathode materials.展开更多
Cation disordering is a common issue in Ni-rich cathodes that significantly degrades cycle life and compromises safety.The cubic rock-salt phase formation and the slow oxidation kinetics of Ni^(2+)during solid-state s...Cation disordering is a common issue in Ni-rich cathodes that significantly degrades cycle life and compromises safety.The cubic rock-salt phase formation and the slow oxidation kinetics of Ni^(2+)during solid-state sintering are widely recognized as the principal causes of these structural defects.To solve this issue,a topotactic soft-chemical precursor engineering strategy is proposed for use in aqueous solution.By utilizing the layered structure of the precursor,this method allows for selective proton extraction and efficient Ni^(2+)oxidation,along with rapid Li+intercalation to form a layered lithiated intermediate.This intermediate crystallizes without further phase transitions during subsequent heat treatment,preventing structural defects caused by complex phase evolution and slow ion diffusion.The resulting cathode exhibits a long-range ordered layered structure and a uniform phase distribution,enabling efficient Li+insertion and extraction.Electrochemical tests reveal a high discharge capacity of 229.6 mAh g^(−1)and an initial coulombic efficiency of 95.77%at 0.1 C,greatly exceeding the performance of a conventionally synthesized cathode(210.3 mAh g^(−1),88.93%).Improved Li^(+)transport kinetics reduces phase-transition hysteresis and alleviates stress concentration,resulting in better cycling stability with a capacity retention of 85.3%after 300 cycles,compared to 61.5%for the conventional sample.This work presents a scalable and effective synthesis route for Ni-rich cathodes with reduced structural disorder and extended lifespan,providing valuable insights into how the regulation of intermediate phases influences electrochemical performance in high-performance Ni-rich cathodes.展开更多
Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_...Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_(2)(PO_(4))_(3)(LVP@C)nanoparticles on carbon nanofibers(CNFs)has been achieved by an electrospinning technique followed by calcination.The protective carbon coating prevents the aggregation of the LVP nanoparticles and suppresses V dissolution by preventing direct contact with aqueous electrolytes.The CNFs derived from the electrospun nanofibers provide a 3D network to increase the electronic conductivity of the LVP electrode,and the LVP@C-CNF hybrid film can be directly used as a freestanding cathode for zinc-ion batteries without adding conductive additives and binders.A mechanism for the formation of a uniform and continuous carbon coating has been proposed.This nanostructure,combined with the uniform and intact carbon coverage,significantly increases the electronic conductivity.This LVP@C-CNF freestanding electrode has an excellent rate capability(47.3%retention at 2 C)and cycling stability(61.2%retention after 100 cycles)within the voltage range 0.6 V to 1.95 V and is highly suitable for zinc-ion battery applications.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
Research on energy storage technology is a vital part of realizing the dual-carbon strategy at this stage.Aqueous zinc-ion batteries(AZIBs)are favorable competitors in various energy storage devices due to their high ...Research on energy storage technology is a vital part of realizing the dual-carbon strategy at this stage.Aqueous zinc-ion batteries(AZIBs)are favorable competitors in various energy storage devices due to their high energy density,reassuring intrinsic safety,and unique cost advantages.The design of cathode materials is crucial for the large-scale development and application of AZIBs.Vanadium-based oxides with high theoretical capacity,diverse valence states,as well as high electrochemical activity,have been widely used as cathode materials for AZIBs.Unfortunately,there are some obstacles,including low electronic conductivity and sluggish kinetics,hindering their further application in AZIBs.In view of the above,this review will introduce a series of modification methods including morphology design,defect engineering,ingenious combination with conductive materials,and modification of electrolyte and zinc anode according to the intrinsic disadvantage of vanadium oxides and summarize the research progress of various modification methods including zinc storage performance and mechanism.Finally,several reasonable prospects will be proposed to appease the needs of basic research and practical applications according to the current status.展开更多
Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active mat...Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.展开更多
Zn-ion batteries(ZIBs) have gained great attention as promising next-generation power sources, because of their low cost, enviable safety and high theoretical capacity. Recently, massive researches have been devoted t...Zn-ion batteries(ZIBs) have gained great attention as promising next-generation power sources, because of their low cost, enviable safety and high theoretical capacity. Recently, massive researches have been devoted to vanadium-based materials as cathodes in ZIBs, owing to their multiple valence states, competitive gravimetric energy density, but the capacity degradation, sluggish kinetics, low operating voltage hinder further optimization of their performance in ZIBs. This review summarizes recent progress to increase the interlayer spacing, structural stability, and the diffusion ability of the vip Zn ions, including the insertion of different ions, introduction of defects, design of diverse morphologies, the combination of other materials. We also focus on approaches to promoting the valuable performance of vanadiumbased cathodes, along with the related ongoing scientific challenges and limitations. Finally, the future perspectives and research directions of vanadium-based aqueous ZIBs are provided.展开更多
Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of lo...Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of low energy&power density and short cycling lifespan owing to the heavy mass and large radius of Na^(+).Vanadium-based polyanionic compounds have advantageous characteristic of high operating voltage,high ionic conductivity and robust structural framework,which is conducive to their high energy&power density and long lifespan for SIBs.In this review,we will overview the latest V-based polyanionic compounds,along with the respective characteristic from the intrinsic crystal structure to performance presentation and improvement for SIBs.One of the most important aspect is to discover the essential problems existed in the present V-based polyanionic compounds for high-energy&power applications,and point out most suitable solutions from the crystal structure modulation,interface tailoring and electrode configuration design.Moreover,some scientific issues of V-based polyanionic compounds shall be also proposed and related future direction shall be provided.We believe that this review can serve as a motivation for further development of novel V-based polyanionic compounds and drive them toward high energy&power applications in the near future.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
Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the ...Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the Jahn-Teller(JT)effect associated with Mn-ion,the cathode exhibits poor structural stability.Herein,we propose a strategy to enhance structural stability by introducing robust metal-oxygen(M-O)bonds,which can realize the pinning effect to constrain the distortion in the transition metal(TM)layer.Concurrently,all the elements employed have exceptionally high crustal abundance.As a proof of concept,the designed K_(0.5)Mn_(0.9)Mg_(0.025)Ti_(0.025)Al_(0.05)O_(2)cathode exhibited a discharge capacity of approximately 100 mA h g^(-1)at 20 mA g^(-1)with 79%capacity retention over 50 cycles,and 73%capacity retention over 200 cycles at 200 mA g^(-1),showcased much better battery performance than the designed cathode with less robust M-O bonds.The properties of the formed M-O bonds were investigated using theoretical calculations.The enhanced dynamics,mitigated JT effect,and improved structural stability were elucidated through the in-situ X-ray diffractometer(XRD),in-situ electrochemical impedance spectroscopy(EIS)(and distribution of relaxation times(DRT)method),and ex-situ X-ray absorption fine structure(XAFS)tests.This study holds substantial reference value for the future design of costeffective Mn-based layered cathodes for PIBs.展开更多
Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cath...Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cathode materials influence the cost and energy output of SIBs.Therefore,the development of advanced cathode materials is crucial for the practical application of SIBs.Among various cathode materials,layered transition metal oxides(LTMOs)have received widespread attention owing to their straightforward preparation,abundant availability,and cost-competitiveness.Notably,layered Fe-based oxide cathodes are deemed to be one of the most promising candidates for the lowest price and easy-to-improve performance.Nevertheless,the challenges such as severe phase transitions,sluggish diffusion kinetics and interfacial degradation pose significant hurdles in achieving high-performance cathodes for SIBs.This review first briefly outlines the classification of layered structures and the working principle of layered oxides.Then,recent advances in modification strategies employed to address current issues with layered iron-based oxide cathodes are systematically reviewed,including ion doping,biphasic engineering and surface modification.Furthermore,the review not only outlines the prospects and development directions for layered Fe-based oxide cathodes but also provides novel insights and directions for future research endeavors for SIBs.展开更多
Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion ...Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion batteries(LIBs).However,parasitic crack formation during the discharge–charge cycling process remains as a major degradation mechanism.Cracking leads to increase in the specific surface area,loss of electrical contact between the primary particles,and facilitates liquid electrolyte infiltration into the cathode active material,accelerating capacity fading and decrease in lifetime.In contrast,Ni-rich NCM when used as a single crystal exhibits superior cycling performances due to its rigid mechanical property that resists cracking during long charge–discharge process even under harsh conditions.In this paper,we present comparative investigation between single crystal Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(SC)and polycrystalline Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(PC).The relatively improved cycling performances of SC are attributed to smaller anisotropic volume change,higher reversibility of phase transition,and resistance to crack formation.The superior properties of SC are demonstrated by in situ characterization and battery tests.Consequently,it is inferred from the results obtained that optimization of preparation conditions can be regarded as a key approach to obtain well crystallized and superior electrochemical performances.展开更多
Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress ...Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress and strain,causes micro-cracks and interfacial contact loss at potentials>4.3 V(vs.Li/Li^(+)).Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxidebased cathodes during electrochemical cycling.Nonetheless,the origin of electrochemical-mechanical damage remains unclear.Herein,We have developed a multifunctional PEG-based soft buffer layer(SBL)on the surface of carbon black(CB).This layer functions as a percolation network in the single crystal LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)and Li_(6)PS_(5)Cl composite cathode layer,ensuring superior ionic conductivity,reducing void formation and particle cracking,and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries(ASSLBs).High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode.This strain produces lattice stretches,distortions,and curved transition metal oxide layers near the surface,contributing to structural degradation at elevated voltages.Consequently,ASSLBs with a LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)cathode containing LCCB-10(CB/PEG mass ratio:100/10)demonstrate a high areal capacity(2.53 mAh g^(-1)/0.32 mA g^(-1))and remarkable rate capability(0.58 mAh g^(-1)at 1.4 mA g^(-1)),with88%capacity retention over 1000 cycles.展开更多
The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructur...The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).展开更多
Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with ne...Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).展开更多
Direct propane dehydrogenation(DPDH)represents a highly attractive route for on-purpose propylene production,a key building block in the petrochemical industry.In particular,among various catalytic platforms,vanadium-...Direct propane dehydrogenation(DPDH)represents a highly attractive route for on-purpose propylene production,a key building block in the petrochemical industry.In particular,among various catalytic platforms,vanadium-based catalysts have emerged as promising candidates due to their tunable properties including redox ability,surface acidity,and resistance to coking.Although the catalytic community has obtained great achievement in this area,how to promote vanadium-based catalysts towards the next step in DPDH applications like industrial-level implementations is still challenging.Moreover,there are still several controversial theories in our community,meaning it is necessary to clarify these indistinct points to pave the way for the next generation of research.Herein,the pivotal modification strategies of vanadium-based catalysts have been summarized via introducing representative works.In addition,the current unclear mechanism and research gaps,especially in the issues of deactivation and selectivity control,are also revealed so that the potential research directions are well-founded proposed.By integrating fundamental understanding and practical considerations,this review aims to inspire the further development of vanadium-based DPDH catalysts for in-depth academic research and next-generation industrial deployment.展开更多
基金supported by the Natural Science Foundation of Tianjin-Science and the Technology Correspondent Project(19YFSLQY00070)the State Key Laboratory of Organic-Inorganic Composites(oic-201901004)+1 种基金the National Natural Science Foundation of China(21676070)Hebei University of Science and Technology(20544401D,20314401D)。
文摘Aqueous zinc-ion batteries(ZIBs)have got wide attention with the increasing demands for energy resource recently.It has a number of merits compared with lithium-ion batteries,such as enhanced safety,low cost and environmental friendliness.Vanadium-based materials have been developed to serve as the cathodes of ZIBs for many years.But there are also some challenges to construct high performance ZIBs in the future.Herein,we reviewed the research progress of vanadium-based cathodes and discussed the energy storage mechanisms in ZIBs.In addition,we summarized the major challenges faced by vanadium-based cathodes and the corresponding ways to improve electrochemical performance of ZIBs.Finally,some excellent vanadium-based cathodes are summarized to pave the way for future research in ZIBs.
基金supported by the National Natural Science Foundation of China (Nos. U1910210, U1810204 and 22004122)Research Foundation for the Returned Overseas in Shanxi Provence (No. 2020-048)the Central Guidance on Local Science and Technology Development Fund of Shanxi Province (No. YDZJSX2021A021)。
文摘As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries(AZIBs) have attracted more and more attention. Vanadium-based compounds are also supposed as the potential candidate cathode materials for AZIBs due to their wide variety of phases, variable crystal structures and high theoretical capacity. In this review, the recent progress in the development of vanadium-based materials was summarized,and the relationship between the crystal structure types of active materials and Zn-ion transport mechanism was highlighted. During the charge-discharge process, the different electrostatic repulsion between the cations of vanadium-based compounds with different crystal structures and Zn^(2+)results in a variety of the Zn-ion storage mechanisms, which can be significant guidance for designing the advanced batteryelectrode materials for AZIBs. Furthermore, other factors associated with the storage mechanisms, such as electrolyte components and electrode morphology, are discussed. Finally, the strategies to improve the electrical conductivity, inhibit the dissolution and stabilize the crystal structure of vanadium-based compounds are proposed and the future prospects for developing high-energy-density AZIBs are presented.
基金financial support from the National Natural Science Foundation of China(No.21676036)the Natural Science Foundation of Chongqing(No.CSTB2023NSCQMSX0580)the Large-scale Equipment Sharing Fund of Chongqing University(No.202403150240 and 202503150091)。
文摘Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.
基金supported by the National Natural Science Foundation of China(NSFC)(22105059,22179078,22479115)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project(B2024204027)+5 种基金the Youth Top-notch Talent Foundation of Hebei Provincial Universities(BJK2022023)the Natural Science Foundation of Hebei Province(B2023204006)the talent training project of Hebei province(No.B20231004)the Innovative Research Team of High-level Local Universities in ShanghaiZhejiang Provincial Natural Science Foundation of China(LY24E020002)Wenzhou basic scientific research project(G20240022)。
文摘Sodium-ion batteries have emerged as promising candidates for next-generation large-scale energy storage systems due to the abundance of sodium resources,low solvation energy,and cost-effectiveness.Among the available cathode materials,vanadium-based sodium phosphate cathodes are particularly notable for their high operating voltage,excellent thermal stability,and superior cycling performance.However,these materials face significant challenges,including sluggish reaction kinetics,the toxicity of vanadium,and poor electronic conductivity.To overcome these limitations and enhance electrochemical performance,various strategies have been explored.These include morphology regulation via diverse synthesis routes and electronic structure optimization through metal doping,which effectively improve the diffusion of Na+and electrons in vanadium-based phosphate cathodes.This review provides a comprehensive overview of the challenges associated with V-based polyanion cathodes and examines the role of morphology and electronic structure design in enhancing performance.Key vanadium-based phosphate frameworks,such as orthophosphates(Na_(3)V_(2)(PO_(4))_(3)),pyrophosphates(NaVP_(2)O_(7),Na_(2)(VO)P_(2)O_(7),Na_(7)V_(3)(P_(2)O_(7))_(4)),and mixed phosphates(Na_(7)V_(4)(P_(2)O_(7))_(4)PO_(4)),are discussed in detail,highlighting recent advances and insights into their structure-property relationships.The design of cathode material morphology offers an effective approach to optimizing material structures,compositions,porosity,and ion/electron diffusion pathways.Simultaneously,electronic structure tuning through element doping allows for the regulation of band structures,electron distribution,diffusion barriers,and the intrinsic conductivity of phosphate compounds.Addressing the challenges associated with vanadium-based sodium phosphate cathode materials,this study proposes feasible solutions and outlines future research directions toward advancement of high-performance vanadium-based polyanion cathodes.
基金supported by the Learning&Academic Research Institution for Master’s,PhD students,and Postdocs LAMP Program of the National Research Foundation of Korea(NRF)grant funded by the Ministry of Education(No.RS-2023-00301974)This work was also supported by the Glocal University 30 Project fund of Gyeongsang National University in 2025.
文摘Lithium manganese silicate(Li-Mn-Si-O)cathodes are key components of lithium-ion batteries,and their physical and mechanical properties are strongly influenced by their underlying crystal structures.In this study,a range of machine learning(ML)algorithms were developed and compared to predict the crystal systems of Li-Mn-Si-O cathode materials using density functional theory(DFT)data obtained from the Materials Project database.The dataset comprised 211 compositions characterized by key descriptors,including formation energy,energy above the hull,bandgap,atomic site number,density,and unit cell volume.These features were utilized to classify the materials into monoclinic(0)and triclinic(1)crystal systems.A comprehensive comparison of various classification algorithms including Decision Tree,Random Forest,XGBoost,Support VectorMachine,k-Nearest Neighbor,Stochastic Gradient Descent,Gaussian Naive Bayes,Gaussian Process,and Artificial Neural Network(ANN)was conducted.Among these,the optimized ANN architecture(6–14-14-14-1)exhibited the highest predictive performance,achieving an accuracy of 95.3%,aMatthews correlation coefficient(MCC)of 0.894,and an F-score of 0.963,demonstrating excellent consistency with DFT-predicted crystal structures.Meanwhile,RandomForest and Gaussian Processmodels also exhibited reliable and consistent predictive capability,indicating their potential as complementary approaches,particularly when data are limited or computational efficiency is required.This comparative framework provides valuable insights into model selection for crystal system classification in complex cathode materials.
基金the financial support from the Central South University Fundamental Research Funds (Grant No.2025ZZTS0444)the Innovation-Driven Research Program(Grant No. 2023 CXQD053)+3 种基金the National Natural Science Foundation of China (Grant No. 52274310)the financial support (Project No.H202111040350002)the provision of the hydroxide precursors from Ningbo Ronbay New Energy Technology Co.,Ltdsupported in part by the High-Performance Computing Center of Central South University
文摘Cation disordering is a common issue in Ni-rich cathodes that significantly degrades cycle life and compromises safety.The cubic rock-salt phase formation and the slow oxidation kinetics of Ni^(2+)during solid-state sintering are widely recognized as the principal causes of these structural defects.To solve this issue,a topotactic soft-chemical precursor engineering strategy is proposed for use in aqueous solution.By utilizing the layered structure of the precursor,this method allows for selective proton extraction and efficient Ni^(2+)oxidation,along with rapid Li+intercalation to form a layered lithiated intermediate.This intermediate crystallizes without further phase transitions during subsequent heat treatment,preventing structural defects caused by complex phase evolution and slow ion diffusion.The resulting cathode exhibits a long-range ordered layered structure and a uniform phase distribution,enabling efficient Li+insertion and extraction.Electrochemical tests reveal a high discharge capacity of 229.6 mAh g^(−1)and an initial coulombic efficiency of 95.77%at 0.1 C,greatly exceeding the performance of a conventionally synthesized cathode(210.3 mAh g^(−1),88.93%).Improved Li^(+)transport kinetics reduces phase-transition hysteresis and alleviates stress concentration,resulting in better cycling stability with a capacity retention of 85.3%after 300 cycles,compared to 61.5%for the conventional sample.This work presents a scalable and effective synthesis route for Ni-rich cathodes with reduced structural disorder and extended lifespan,providing valuable insights into how the regulation of intermediate phases influences electrochemical performance in high-performance Ni-rich cathodes.
文摘Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_(2)(PO_(4))_(3)(LVP@C)nanoparticles on carbon nanofibers(CNFs)has been achieved by an electrospinning technique followed by calcination.The protective carbon coating prevents the aggregation of the LVP nanoparticles and suppresses V dissolution by preventing direct contact with aqueous electrolytes.The CNFs derived from the electrospun nanofibers provide a 3D network to increase the electronic conductivity of the LVP electrode,and the LVP@C-CNF hybrid film can be directly used as a freestanding cathode for zinc-ion batteries without adding conductive additives and binders.A mechanism for the formation of a uniform and continuous carbon coating has been proposed.This nanostructure,combined with the uniform and intact carbon coverage,significantly increases the electronic conductivity.This LVP@C-CNF freestanding electrode has an excellent rate capability(47.3%retention at 2 C)and cycling stability(61.2%retention after 100 cycles)within the voltage range 0.6 V to 1.95 V and is highly suitable for zinc-ion battery applications.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
基金financially supported by the National Nature Science Foundation of China(No.51562006)Guangxi Distinguished Experts Special Fund(No.2019B06)the Innovation Project of Guangxi Graduate Education(No.SC2200000985)。
文摘Research on energy storage technology is a vital part of realizing the dual-carbon strategy at this stage.Aqueous zinc-ion batteries(AZIBs)are favorable competitors in various energy storage devices due to their high energy density,reassuring intrinsic safety,and unique cost advantages.The design of cathode materials is crucial for the large-scale development and application of AZIBs.Vanadium-based oxides with high theoretical capacity,diverse valence states,as well as high electrochemical activity,have been widely used as cathode materials for AZIBs.Unfortunately,there are some obstacles,including low electronic conductivity and sluggish kinetics,hindering their further application in AZIBs.In view of the above,this review will introduce a series of modification methods including morphology design,defect engineering,ingenious combination with conductive materials,and modification of electrolyte and zinc anode according to the intrinsic disadvantage of vanadium oxides and summarize the research progress of various modification methods including zinc storage performance and mechanism.Finally,several reasonable prospects will be proposed to appease the needs of basic research and practical applications according to the current status.
基金supported by the National Natural Science Foundation of China(51962002)the Natural Science Foundation of Guangxi(2022GXNSFAA035463)the National Key R&D Program of China(2022YFB2404402)。
文摘Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.
基金financially supported by the State Key Lab of Advanced Metals and Materials (No. 2020-Z14)the Startup Funds from the Henan University of Science and Technology (Nos. 13480095 and 13480096)the National Natural Science Foundation of China (No. 52002119)。
文摘Zn-ion batteries(ZIBs) have gained great attention as promising next-generation power sources, because of their low cost, enviable safety and high theoretical capacity. Recently, massive researches have been devoted to vanadium-based materials as cathodes in ZIBs, owing to their multiple valence states, competitive gravimetric energy density, but the capacity degradation, sluggish kinetics, low operating voltage hinder further optimization of their performance in ZIBs. This review summarizes recent progress to increase the interlayer spacing, structural stability, and the diffusion ability of the vip Zn ions, including the insertion of different ions, introduction of defects, design of diverse morphologies, the combination of other materials. We also focus on approaches to promoting the valuable performance of vanadiumbased cathodes, along with the related ongoing scientific challenges and limitations. Finally, the future perspectives and research directions of vanadium-based aqueous ZIBs are provided.
基金financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21070500)the DNL Cooperation Fund,CAS(DNL201914)。
文摘Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of low energy&power density and short cycling lifespan owing to the heavy mass and large radius of Na^(+).Vanadium-based polyanionic compounds have advantageous characteristic of high operating voltage,high ionic conductivity and robust structural framework,which is conducive to their high energy&power density and long lifespan for SIBs.In this review,we will overview the latest V-based polyanionic compounds,along with the respective characteristic from the intrinsic crystal structure to performance presentation and improvement for SIBs.One of the most important aspect is to discover the essential problems existed in the present V-based polyanionic compounds for high-energy&power applications,and point out most suitable solutions from the crystal structure modulation,interface tailoring and electrode configuration design.Moreover,some scientific issues of V-based polyanionic compounds shall be also proposed and related future direction shall be provided.We believe that this review can serve as a motivation for further development of novel V-based polyanionic compounds and drive them toward high energy&power applications in the near future.
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financially supported by the National Natural Science Foundation of China(NSFC)(52274295)the Natural Science Foundation of Hebei Province(E2021501029)+3 种基金the Fundamental Research Funds for the Central Universities(N2423051,N2423053,N2302016,N2423019,N2323013,N2423005)the Science and Technology Project of Hebei Education Department(QN2024238)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)the Science and Technology Project of Qinhuangdao City in 2023.
文摘Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the Jahn-Teller(JT)effect associated with Mn-ion,the cathode exhibits poor structural stability.Herein,we propose a strategy to enhance structural stability by introducing robust metal-oxygen(M-O)bonds,which can realize the pinning effect to constrain the distortion in the transition metal(TM)layer.Concurrently,all the elements employed have exceptionally high crustal abundance.As a proof of concept,the designed K_(0.5)Mn_(0.9)Mg_(0.025)Ti_(0.025)Al_(0.05)O_(2)cathode exhibited a discharge capacity of approximately 100 mA h g^(-1)at 20 mA g^(-1)with 79%capacity retention over 50 cycles,and 73%capacity retention over 200 cycles at 200 mA g^(-1),showcased much better battery performance than the designed cathode with less robust M-O bonds.The properties of the formed M-O bonds were investigated using theoretical calculations.The enhanced dynamics,mitigated JT effect,and improved structural stability were elucidated through the in-situ X-ray diffractometer(XRD),in-situ electrochemical impedance spectroscopy(EIS)(and distribution of relaxation times(DRT)method),and ex-situ X-ray absorption fine structure(XAFS)tests.This study holds substantial reference value for the future design of costeffective Mn-based layered cathodes for PIBs.
基金supported by the National Natural Science Foundation of China(no.52374301)the Open Project of Guangxi Key Laboratory of Electrochemical Energy Materials(no.GXUEEM2024001)+2 种基金the Hebei Provincial Natural Science Foundation(no.E2024501010)the Shijiazhuang Basic Research Project(no.241790667A)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)。
文摘Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cathode materials influence the cost and energy output of SIBs.Therefore,the development of advanced cathode materials is crucial for the practical application of SIBs.Among various cathode materials,layered transition metal oxides(LTMOs)have received widespread attention owing to their straightforward preparation,abundant availability,and cost-competitiveness.Notably,layered Fe-based oxide cathodes are deemed to be one of the most promising candidates for the lowest price and easy-to-improve performance.Nevertheless,the challenges such as severe phase transitions,sluggish diffusion kinetics and interfacial degradation pose significant hurdles in achieving high-performance cathodes for SIBs.This review first briefly outlines the classification of layered structures and the working principle of layered oxides.Then,recent advances in modification strategies employed to address current issues with layered iron-based oxide cathodes are systematically reviewed,including ion doping,biphasic engineering and surface modification.Furthermore,the review not only outlines the prospects and development directions for layered Fe-based oxide cathodes but also provides novel insights and directions for future research endeavors for SIBs.
基金supported by the Technology Innovation Program(RS-2023-00256202Development of MLCB design and manufacturing process technology for board mounting)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)+2 种基金supported by the Technology Innovation Program(or Industrial Strategic Technology Development Program-Public-private joint investment semiconductor R&D program(K-CHIPS)to foster high-quality human resources)(RS-2023-00237003,High selectivity etching technology using cryoetch)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by 2022 Research Grant from Kangwon National University(No.202203080001)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2023-00280367).
文摘Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion batteries(LIBs).However,parasitic crack formation during the discharge–charge cycling process remains as a major degradation mechanism.Cracking leads to increase in the specific surface area,loss of electrical contact between the primary particles,and facilitates liquid electrolyte infiltration into the cathode active material,accelerating capacity fading and decrease in lifetime.In contrast,Ni-rich NCM when used as a single crystal exhibits superior cycling performances due to its rigid mechanical property that resists cracking during long charge–discharge process even under harsh conditions.In this paper,we present comparative investigation between single crystal Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(SC)and polycrystalline Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(PC).The relatively improved cycling performances of SC are attributed to smaller anisotropic volume change,higher reversibility of phase transition,and resistance to crack formation.The superior properties of SC are demonstrated by in situ characterization and battery tests.Consequently,it is inferred from the results obtained that optimization of preparation conditions can be regarded as a key approach to obtain well crystallized and superior electrochemical performances.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2021SHFZ232,ZDYF2023GXJS022)the Hainan Province Postdoctoral Science Foundation(300333)the National Natural Science Foundation of China(21203008,21975025,12274025,22372008)。
文摘Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress and strain,causes micro-cracks and interfacial contact loss at potentials>4.3 V(vs.Li/Li^(+)).Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxidebased cathodes during electrochemical cycling.Nonetheless,the origin of electrochemical-mechanical damage remains unclear.Herein,We have developed a multifunctional PEG-based soft buffer layer(SBL)on the surface of carbon black(CB).This layer functions as a percolation network in the single crystal LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)and Li_(6)PS_(5)Cl composite cathode layer,ensuring superior ionic conductivity,reducing void formation and particle cracking,and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries(ASSLBs).High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode.This strain produces lattice stretches,distortions,and curved transition metal oxide layers near the surface,contributing to structural degradation at elevated voltages.Consequently,ASSLBs with a LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)cathode containing LCCB-10(CB/PEG mass ratio:100/10)demonstrate a high areal capacity(2.53 mAh g^(-1)/0.32 mA g^(-1))and remarkable rate capability(0.58 mAh g^(-1)at 1.4 mA g^(-1)),with88%capacity retention over 1000 cycles.
基金supported by the National Key R&D Program of China(2022YFB3803501)the National Natural Science Foundation of China(22179008,22209156)+5 种基金support from the Beijing Nova Program(20230484241)support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)support from beamline BL08U1A of Shanghai Synchrotron Radiation Facility(2024-SSRF-PT-506950)beamline 1W1B of the Beijing Synchrotron Radiation Facility(2021-BEPC-PT-006276)support from Initial Energy Science&Technology Co.,Ltd(IEST)。
文摘The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).
基金supported by the research project within the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,Action 21)Kun Zheng acknowledges financial support from AGH University of Krakow(No.16.16.210.476).
文摘Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).
基金support from Liaoning Revitalization Talents Program(XLYC2203068)National Natural Science Foundation of China(21902116)2024 Fundamental Research Funding of the Educational Department of Liaoning Province.Y.L.acknowledges the Program of China Scholarships Council(No.202206250016).
文摘Direct propane dehydrogenation(DPDH)represents a highly attractive route for on-purpose propylene production,a key building block in the petrochemical industry.In particular,among various catalytic platforms,vanadium-based catalysts have emerged as promising candidates due to their tunable properties including redox ability,surface acidity,and resistance to coking.Although the catalytic community has obtained great achievement in this area,how to promote vanadium-based catalysts towards the next step in DPDH applications like industrial-level implementations is still challenging.Moreover,there are still several controversial theories in our community,meaning it is necessary to clarify these indistinct points to pave the way for the next generation of research.Herein,the pivotal modification strategies of vanadium-based catalysts have been summarized via introducing representative works.In addition,the current unclear mechanism and research gaps,especially in the issues of deactivation and selectivity control,are also revealed so that the potential research directions are well-founded proposed.By integrating fundamental understanding and practical considerations,this review aims to inspire the further development of vanadium-based DPDH catalysts for in-depth academic research and next-generation industrial deployment.
