Although significant progress has been made in many aspects of the emerging aprotic Li-O2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the posit...Although significant progress has been made in many aspects of the emerging aprotic Li-O2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O2 batteries from the conventional Li-ion cells and play a crucial role in the Li-O2 cell＇s performance （capacity, rate capability, and cycle life）. Recent advances in fundamental studies of oxygen reactions in aprotic Li-O2 batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li2O2, and charge transport within Li2O2. Prospects are also provided for future fundamental investigations of Li-O2 chemistry.展开更多
Nonaqueous Li-O2 batteries attract attention for their theoretical specific energy density.However,due to the difficulty of decomposition of Li2 O2,Li-O2 batteries have high charge overpotential and poor cycling life....Nonaqueous Li-O2 batteries attract attention for their theoretical specific energy density.However,due to the difficulty of decomposition of Li2 O2,Li-O2 batteries have high charge overpotential and poor cycling life.So all kinds of catalysts have been studied on the cathode.Compared to heterogeneous solid catalysts,soluble catalysts achieve faster and more effective transport of electrons by reversible redox pairs.Here,we first report ruthenocene(Ruc) as a mobile redox mediator in a Li-O2 battery.0.01 mol/L Ruc in the electrolyte effectively reduces the charging voltage by 610 mV.Additionally,Ruc greatly increases the cycling life by four-fold(up to 83 cycles) with a simple ketjen black(KB) cathode.The results of SEM,XPS and XRD confirm that less discharge product residue accumulated after recharge.To verify the reaction mechanisms of the mediato r,free energy profiles of the possible reaction pathways based on DFT are provided.展开更多
As one of the next-generation energy-storage devices,Li-O_2 battery has become the main research direction for the academic researchers due to its characteristics of environmental friendship,relatively simple structur...As one of the next-generation energy-storage devices,Li-O_2 battery has become the main research direction for the academic researchers due to its characteristics of environmental friendship,relatively simple structures,high energy density of 3500Wh/kg and low cost.However,Li-O_2 battery cannot be commercialized on a large scale because of the challenging issues including high-efficient electrocatalysts,membranes,Li-based anode and so on.In this review,we focused on the recent development of electrocatalyst materials as cathodes for the non-aqueous Li-O_2 batteries which are relatively simpler than other Li-O_2 batteries＇ structures.Electrocatalysts were summarized including noble metals,nanocarbon materials,transition metals and their hybrids.We points out that the challenges of preparation high-efficient catalysts not only require high catalytic activity and conductivity,but also have novel nanoarchitectures with large interface and porous volume for LiO_x storage.Furthermore,the further investigation of reaction mechanism and advanced in situ analysis technologies are welcome in the coming work.展开更多
Developing bifunctional catalysts that increase both the OER and ORR kinetics and transport reactants with high efficiency is desirable. Herein, micro–meso-macroporous FeCo-N-C-X(denoted as "MFeCo-N-C-X", X...Developing bifunctional catalysts that increase both the OER and ORR kinetics and transport reactants with high efficiency is desirable. Herein, micro–meso-macroporous FeCo-N-C-X(denoted as "MFeCo-N-C-X", X represents Fe/Co molar ratio in bimetallic zeolite imidazole frameworks FeCo-ZIFs) catalysts derived from hierarchical M-FeCo-ZIFs-X was prepared. The micropores in M-FeCo-N-C-X have strong capability in O2 capture as well as dictate the nucleation and early-stage deposition of Li2O2,the mesopores provided a channel for the electrolyte wetting, and the macroporous structure promoted more available active sites when used as cathode for Li-O2 batteries. More importantly, M-Fe CoN-C-0.2 based cathode showed a high initial capacity(18,750 mAh g-1@0.1 A g-1), good rate capability(7900 m Ah g-1@0.5 A g-1), and cycle stability up to 192 cycles. Interestingly, the FeCo-N-C-0.2 without macropores suffered relatively poorer stability with only 75 cycles, although its discharge capacity was still as high as 17,200 mA h g-1(@0.1 A g-1). The excellent performance attributed to the synergistic contribution of homogeneous Fe, Co nanoparticles and N co-doping carbon frameworks with special micro–meso-macroporous structure. The results showed that hierarchical FeCo-N-C architectures are promising cathode catalysts for Li-O2 batteries.展开更多
Despite their high theoretical capacity and energy density,lithiumsulfur(Li–S)batteries still face challenges such as soluble lithium polysulfides(LiPSs)shuttling and sluggish redox kinetics.In this work,we used a no...Despite their high theoretical capacity and energy density,lithiumsulfur(Li–S)batteries still face challenges such as soluble lithium polysulfides(LiPSs)shuttling and sluggish redox kinetics.In this work,we used a novel MoS_(2)-Mo_(2)C heterostructure anchored on a carbon sponge(CS)as a Li_(2)S host to solve these problems.A simple hydrothermal process following carbothermal reduction was used to construct the MoS_(2)-Mo_(2)C heterostructure,enabling control of the phases and integration of MoS_(2) and Mo_(2)C.Structural characterization confirmed the coherent interface of the heterostructure with a precise orientation relationship between the two phases and their uniform distribution.An evaluation of the adsorption and catalytic performance of the material showed that it has an exceptional LiPSs adsorption capacity with faster conversion from Li_(2)S_(4) to Li_(2)S_(2).Density functional theory calculations further confirmed these results.As a result,the cathode had a high initial discharge capacity of 693 mAh g^(−1) at 0.2 C and achieved stable cycling at 2 C for 500 cycles with a low decay rate of 0.107%per cycle.The heterostructure design,coupled with the macroporous CS framework,effectively prevented the shuttling and increased sulfur utilization,offering a promising way to produce practical high-energydensity Li–S batteries.展开更多
Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by t...Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by the poor conductivity andthe irreversible dissolution of conventionalε-MnO_(2)deposits.Herein,we report a scalable semisolid slurryelectrode architecture that enables stable MnO_(2)deposition/dissolution using a three-dimensional percolatingnetwork of carbon nanotubes(CNTs)as both conductivematrix and deposition host.The slurry systempromotes the formation of highly conductiveγ-MnO_(2)owing to enhanced charge transfer kinetics,enablingoverall dissolution rather than the localized separationtypically seen in traditional electrodes.The Zn-MnO_(2)slurry cell exhibits a reversible areal capacity approaching 60 mAh cm^(-2).Moreover,theflowable nature of the slurry allows electrochemically inactive MnO_(2)formed during dissolution to be reconnected and reactivated by CNTs inthe rheological network,ensuring deep utilization and cycling stability.This work establishes a slurry electrode strategy to improve electrolyticMnO_(2)reactions and offers a viable pathway toward renewable aqueous batteries for grid-scale applications.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
Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challeng...Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.展开更多
Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen ba...Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.展开更多
Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on ...Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.展开更多
TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperat...TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.展开更多
Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosize...Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.展开更多
Low-cost and high-safety aqueous Zn-I_(2) batteries attract extensive attention for large-scale energy storage systems.However,polyiodide shuttling and sluggish iodine conversion reactions lead to inferior rate capabi...Low-cost and high-safety aqueous Zn-I_(2) batteries attract extensive attention for large-scale energy storage systems.However,polyiodide shuttling and sluggish iodine conversion reactions lead to inferior rate capability and severe capacity decay.Herein,a three-dimensional polyaniline is wrapped by carboxylcarbon nanotubes(denoted as C-PANI)which is designed as a catalytic cathode to effectively boost iodine conversion with suppressed polyiodide shuttling,thereby improving Zn-I_(2) batteries.Specifically,carboxyl-carbon nanotubes serve as a proton reservoir for more protonated-NH+=sites in PANI chains,achieving a direct I0/I−reaction for suppressed polyiodide generation and Zn corrosion.Attributing to this“proton-iodine”regulation,catalytic protonated C-PANI strongly fixes electrolytic iodine species and stores proton ions simultaneously through reversible-N=/-NH^(+)-reaction.Therefore,the electrolytic Zn-I_(2) battery with C-PANI cathode exhibits an impressive capacity of 420 mAh g^(−1) and ultra-long lifespan over 40,000 cycles.Additionally,a 60 mAh pouch cell was assembled with excellent cycling stability after 100 cycles,providing new insights into exploring effective organocatalysts for superb Zn-halogen batteries.展开更多
NASICON-type Na_(3)V_(2)(PO_(4))_(3)(NVP)materials are seen as highly promising cathode materials in the field of sodium-ion batteries due to their low cost,a solid three-dimensional skeleton and good theoretical capa...NASICON-type Na_(3)V_(2)(PO_(4))_(3)(NVP)materials are seen as highly promising cathode materials in the field of sodium-ion batteries due to their low cost,a solid three-dimensional skeleton and good theoretical capacity,as well as high ionic conductivity.Nevertheless,the problem of low intrinsic electronic conductivity and energy density has limited the practical application of the materials.To address this issue,the relevant research team has successfully achieved remarkable research results through unremitting exploration and practical innovation.In this work,the crystal structure,ion migration mechanism and sodium storage mechanism of NVP cathode materials are systematically reviewed,with a focus on summarizing the latest progress of V-site doping modification research,classifying and exploring V-site doping from the perspectives of electronic structure,lattice strain and entropy,and briefly describing the optimization mechanism of V-site doping on electrochemical performance.In addition,the challenges and prospects for the future development of NVP cathode materials are presented,which are believed to provide new thinking for the design and development of high-performance NVP cathode materials and contribute to the large-scale application of sodium-ion batteries.展开更多
The metal triazole(MTA)-based MOFs were found to preferentially adsorb O-rich species,which had enhanced electrocatalytic oxygen reduction reactions(ORR)and stabilized the O-containing species during the discharge and...The metal triazole(MTA)-based MOFs were found to preferentially adsorb O-rich species,which had enhanced electrocatalytic oxygen reduction reactions(ORR)and stabilized the O-containing species during the discharge and charge processes in Li-O_(2)battery.However,the MOFs exhibited low electron conductivity and poor electron transfer interface in the electrocatalysis,limiting the electrocatalytic activity.To address this issue,a nanocomposite with the Co-MTA-coated carbon nano tubes(Co-MTA-C)was constructed,which formed the three-dimensional conductivity network connected with the intersecting carbon nano tube(CNT).In this composite,the electron-rich Co-MTA interacted with the highly conductive CNT,resulting in a charge redistribution.Optimized the electronic structure of the Co center through compositional modifications presented a high valence compared to the pure MOFs.In situ X-ray absorption spectroscopy revealed a direct reaction of Co sites with intermediates such as LiO_(x),leading to the formation of nanosheet array discharge products.The battery based on optimized CoMTA-C demonstrated fast kinetics and superior stability,with a low overpotential of 1.13 V,high specific capacity of 9057 mAh g^(-1),and long-term durability of 600 cycles.It provides a facile and effective strategy for enhancing the electrocatalytic performance through rational tuning of high-conductivity substances.展开更多
Science 2015,350,530-533Rechargeable lithium-air（Li-O2）batteries have received considerable attentions due to their much higher theoretical energy densities than today’s lithium-ion batteries.However,they still suf...Science 2015,350,530-533Rechargeable lithium-air（Li-O2）batteries have received considerable attentions due to their much higher theoretical energy densities than today’s lithium-ion batteries.However,they still suffer from at least four limitations:（1）much lower capacity than theoretical capacity,stemming from the small pore sizes and volumes of the current porous electrode;（2）side reactions,including electrode materials,electrolyte,intermediate and final discharge products;（3）large展开更多
Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in...Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.展开更多
Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stab...Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.展开更多
Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degra...Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degradation at high current densities.We address these issues by a“killing two birds with one stone”O_(2)-pressure protocol.It first resolves efficient O_(2) mass transport at high rates..The accelerated reaction kinetics optimizes the composition and growth pathway of discharge products.This protocol secondly achieves protection of Li anodes via densifying corrosion layers on them.Consequently,the battery delivers both ultrahigh discharge capacity(>9,000 mAh g^(-1))at 3,000 mA g^(-1) and excellent cycling stability.Under a dual-strategy effect of high-pressure O_(2) and artificial protection layers,the battery actualizes over 11-fold increase in cycle life of 5,170 h(2,585 cycles).The strategy opens avenues for advancing Li-O_(2) batteries towards practical application and confers the extension to other gas-based batteries.展开更多
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
基金supported by the Recruitment Program of Global Youth Experts of Chinathe Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA09010401)+1 种基金the Science and Technology Development Program of Jilin Province,China(Grant No.20150623002TC)the Natural Science Foundation of Jiangsu Province,China(Grant No.BK20131139)
文摘Although significant progress has been made in many aspects of the emerging aprotic Li-O2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O2 batteries from the conventional Li-ion cells and play a crucial role in the Li-O2 cell＇s performance （capacity, rate capability, and cycle life）. Recent advances in fundamental studies of oxygen reactions in aprotic Li-O2 batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li2O2, and charge transport within Li2O2. Prospects are also provided for future fundamental investigations of Li-O2 chemistry.
基金the National Natural Science Foundation of China (Nos.U1732111 and 21676241)“The Recruitment Program of Global Youth Experts” from the Chinese government+2 种基金the “Hundred Talents Program” of Zhejiang UniversityHubei Natural Science Foundation of China (No.2018CFB531)Self-determined Research Funds of CCNU from Colleges’ Basic Research and Operation of MOE (No.CCNU18TS045)。
文摘Nonaqueous Li-O2 batteries attract attention for their theoretical specific energy density.However,due to the difficulty of decomposition of Li2 O2,Li-O2 batteries have high charge overpotential and poor cycling life.So all kinds of catalysts have been studied on the cathode.Compared to heterogeneous solid catalysts,soluble catalysts achieve faster and more effective transport of electrons by reversible redox pairs.Here,we first report ruthenocene(Ruc) as a mobile redox mediator in a Li-O2 battery.0.01 mol/L Ruc in the electrolyte effectively reduces the charging voltage by 610 mV.Additionally,Ruc greatly increases the cycling life by four-fold(up to 83 cycles) with a simple ketjen black(KB) cathode.The results of SEM,XPS and XRD confirm that less discharge product residue accumulated after recharge.To verify the reaction mechanisms of the mediato r,free energy profiles of the possible reaction pathways based on DFT are provided.
基金supported by the Natural Science Foundation of China(No.21303038)Scientific Research Foundation for the Returned Overseas Chinese Scholars+1 种基金State Education Ministry One Hundred,Talents Program of Anhui ProvinceOpen Funds of the State Key Laboratory of Rare Earth Resource Utilization(No.RERU2016004)
文摘As one of the next-generation energy-storage devices,Li-O_2 battery has become the main research direction for the academic researchers due to its characteristics of environmental friendship,relatively simple structures,high energy density of 3500Wh/kg and low cost.However,Li-O_2 battery cannot be commercialized on a large scale because of the challenging issues including high-efficient electrocatalysts,membranes,Li-based anode and so on.In this review,we focused on the recent development of electrocatalyst materials as cathodes for the non-aqueous Li-O_2 batteries which are relatively simpler than other Li-O_2 batteries＇ structures.Electrocatalysts were summarized including noble metals,nanocarbon materials,transition metals and their hybrids.We points out that the challenges of preparation high-efficient catalysts not only require high catalytic activity and conductivity,but also have novel nanoarchitectures with large interface and porous volume for LiO_x storage.Furthermore,the further investigation of reaction mechanism and advanced in situ analysis technologies are welcome in the coming work.
基金sponsored by the National Natural Science Foundation of China(21475021 and 21427807)the Fundamental Research Funds for the Central Universities(2242017 K41023)
文摘Developing bifunctional catalysts that increase both the OER and ORR kinetics and transport reactants with high efficiency is desirable. Herein, micro–meso-macroporous FeCo-N-C-X(denoted as "MFeCo-N-C-X", X represents Fe/Co molar ratio in bimetallic zeolite imidazole frameworks FeCo-ZIFs) catalysts derived from hierarchical M-FeCo-ZIFs-X was prepared. The micropores in M-FeCo-N-C-X have strong capability in O2 capture as well as dictate the nucleation and early-stage deposition of Li2O2,the mesopores provided a channel for the electrolyte wetting, and the macroporous structure promoted more available active sites when used as cathode for Li-O2 batteries. More importantly, M-Fe CoN-C-0.2 based cathode showed a high initial capacity(18,750 mAh g-1@0.1 A g-1), good rate capability(7900 m Ah g-1@0.5 A g-1), and cycle stability up to 192 cycles. Interestingly, the FeCo-N-C-0.2 without macropores suffered relatively poorer stability with only 75 cycles, although its discharge capacity was still as high as 17,200 mA h g-1(@0.1 A g-1). The excellent performance attributed to the synergistic contribution of homogeneous Fe, Co nanoparticles and N co-doping carbon frameworks with special micro–meso-macroporous structure. The results showed that hierarchical FeCo-N-C architectures are promising cathode catalysts for Li-O2 batteries.
文摘Despite their high theoretical capacity and energy density,lithiumsulfur(Li–S)batteries still face challenges such as soluble lithium polysulfides(LiPSs)shuttling and sluggish redox kinetics.In this work,we used a novel MoS_(2)-Mo_(2)C heterostructure anchored on a carbon sponge(CS)as a Li_(2)S host to solve these problems.A simple hydrothermal process following carbothermal reduction was used to construct the MoS_(2)-Mo_(2)C heterostructure,enabling control of the phases and integration of MoS_(2) and Mo_(2)C.Structural characterization confirmed the coherent interface of the heterostructure with a precise orientation relationship between the two phases and their uniform distribution.An evaluation of the adsorption and catalytic performance of the material showed that it has an exceptional LiPSs adsorption capacity with faster conversion from Li_(2)S_(4) to Li_(2)S_(2).Density functional theory calculations further confirmed these results.As a result,the cathode had a high initial discharge capacity of 693 mAh g^(−1) at 0.2 C and achieved stable cycling at 2 C for 500 cycles with a low decay rate of 0.107%per cycle.The heterostructure design,coupled with the macroporous CS framework,effectively prevented the shuttling and increased sulfur utilization,offering a promising way to produce practical high-energydensity Li–S batteries.
基金supported by the National Natural Science Foundation of China(No.22109181,U24A2060,22279023,and 22309031)the National Key R&D Program of China(2024YFE0101100)+6 种基金the Hunan Provincial Science and Technology Plan Projects of China(No.2017TP1001)the Hunan Provincial Natural Science Foundation of China(No.2025JJ40011)the Fundamental Research Funds for the Central Universities(20720250005)the Science and Technology Commission of Shanghai Municipality(25DZ3002901,2024ZDSYS02,25PY2600100)the Shanghai Pilot Program for Basic Research-Fudan University 21TQ1400100(25TQ012)the AI for Science Foundation of Fudan University(FudanX24A1035)the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by the poor conductivity andthe irreversible dissolution of conventionalε-MnO_(2)deposits.Herein,we report a scalable semisolid slurryelectrode architecture that enables stable MnO_(2)deposition/dissolution using a three-dimensional percolatingnetwork of carbon nanotubes(CNTs)as both conductivematrix and deposition host.The slurry systempromotes the formation of highly conductiveγ-MnO_(2)owing to enhanced charge transfer kinetics,enablingoverall dissolution rather than the localized separationtypically seen in traditional electrodes.The Zn-MnO_(2)slurry cell exhibits a reversible areal capacity approaching 60 mAh cm^(-2).Moreover,theflowable nature of the slurry allows electrochemically inactive MnO_(2)formed during dissolution to be reconnected and reactivated by CNTs inthe rheological network,ensuring deep utilization and cycling stability.This work establishes a slurry electrode strategy to improve electrolyticMnO_(2)reactions and offers a viable pathway toward renewable aqueous batteries for grid-scale applications.
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supported by the “Pioneer” and “Leading Goose” R&D Program of Zhejiang Province of China (No. 2024C01056)the support from London South Bank University
文摘Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.
基金financially supported by the National Natural Science Foundation of China(U21A20311,U24A2040,52171141,52272117)the Natural Science Foundation of Shandong Province(ZR2022JQ19)+3 种基金the Key Technology Research Project of Shandong Province(2023CXGC010202)the Taishan Industrial Experts Program(TSCX202306142)the Core Facility Sharing Platform of Shandong Universitythe Foundation of Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University。
文摘Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.
基金supported by the Foundation of Yunnan Province(Nos.202301AU070021,202201BE070001-027)the Test Foundation of KUST(No.2022T20210208).
文摘Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(22279026,2247090373)the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1401)+2 种基金the China Postdoctoral Science Foundation(2024M764198)the National Natural Science Foundation of China(22509044)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the Fundamental Research Funds for the Central Universities(No.2024CDJXY003)+1 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2023087)The Chongqing Technology Innovation and Application Development Project(No.2024TIAD-KPX0003).
文摘Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.
基金supported by the National Natural Science Foundation of China(22209006,21935001)the Natural Science Foundation of Shandong Province(ZR2022QE009)+1 种基金Fundamental Research Funds for the Central Universities(buctrc202307)the Beijing Natural Science Foundation(Z210016).
文摘Low-cost and high-safety aqueous Zn-I_(2) batteries attract extensive attention for large-scale energy storage systems.However,polyiodide shuttling and sluggish iodine conversion reactions lead to inferior rate capability and severe capacity decay.Herein,a three-dimensional polyaniline is wrapped by carboxylcarbon nanotubes(denoted as C-PANI)which is designed as a catalytic cathode to effectively boost iodine conversion with suppressed polyiodide shuttling,thereby improving Zn-I_(2) batteries.Specifically,carboxyl-carbon nanotubes serve as a proton reservoir for more protonated-NH+=sites in PANI chains,achieving a direct I0/I−reaction for suppressed polyiodide generation and Zn corrosion.Attributing to this“proton-iodine”regulation,catalytic protonated C-PANI strongly fixes electrolytic iodine species and stores proton ions simultaneously through reversible-N=/-NH^(+)-reaction.Therefore,the electrolytic Zn-I_(2) battery with C-PANI cathode exhibits an impressive capacity of 420 mAh g^(−1) and ultra-long lifespan over 40,000 cycles.Additionally,a 60 mAh pouch cell was assembled with excellent cycling stability after 100 cycles,providing new insights into exploring effective organocatalysts for superb Zn-halogen batteries.
基金supported by the National Natural Science Foundation of China(no.52574348)the Natural Science Foundation of Hebei Province(no.B2024501004)+2 种基金the Fundamental Research Funds for the Central Universities(no.N2423013)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NASICON-type Na_(3)V_(2)(PO_(4))_(3)(NVP)materials are seen as highly promising cathode materials in the field of sodium-ion batteries due to their low cost,a solid three-dimensional skeleton and good theoretical capacity,as well as high ionic conductivity.Nevertheless,the problem of low intrinsic electronic conductivity and energy density has limited the practical application of the materials.To address this issue,the relevant research team has successfully achieved remarkable research results through unremitting exploration and practical innovation.In this work,the crystal structure,ion migration mechanism and sodium storage mechanism of NVP cathode materials are systematically reviewed,with a focus on summarizing the latest progress of V-site doping modification research,classifying and exploring V-site doping from the perspectives of electronic structure,lattice strain and entropy,and briefly describing the optimization mechanism of V-site doping on electrochemical performance.In addition,the challenges and prospects for the future development of NVP cathode materials are presented,which are believed to provide new thinking for the design and development of high-performance NVP cathode materials and contribute to the large-scale application of sodium-ion batteries.
基金financially supported by the National Natural Science Foundations of China(No.12304037)the Interdisciplinary Intelligence Super Computer Center of BNUZH
文摘The metal triazole(MTA)-based MOFs were found to preferentially adsorb O-rich species,which had enhanced electrocatalytic oxygen reduction reactions(ORR)and stabilized the O-containing species during the discharge and charge processes in Li-O_(2)battery.However,the MOFs exhibited low electron conductivity and poor electron transfer interface in the electrocatalysis,limiting the electrocatalytic activity.To address this issue,a nanocomposite with the Co-MTA-coated carbon nano tubes(Co-MTA-C)was constructed,which formed the three-dimensional conductivity network connected with the intersecting carbon nano tube(CNT).In this composite,the electron-rich Co-MTA interacted with the highly conductive CNT,resulting in a charge redistribution.Optimized the electronic structure of the Co center through compositional modifications presented a high valence compared to the pure MOFs.In situ X-ray absorption spectroscopy revealed a direct reaction of Co sites with intermediates such as LiO_(x),leading to the formation of nanosheet array discharge products.The battery based on optimized CoMTA-C demonstrated fast kinetics and superior stability,with a low overpotential of 1.13 V,high specific capacity of 9057 mAh g^(-1),and long-term durability of 600 cycles.It provides a facile and effective strategy for enhancing the electrocatalytic performance through rational tuning of high-conductivity substances.
文摘Science 2015,350,530-533Rechargeable lithium-air（Li-O2）batteries have received considerable attentions due to their much higher theoretical energy densities than today’s lithium-ion batteries.However,they still suffer from at least four limitations:（1）much lower capacity than theoretical capacity,stemming from the small pore sizes and volumes of the current porous electrode;（2）side reactions,including electrode materials,electrolyte,intermediate and final discharge products;（3）large
基金supported by the Natural Sci-ence Foundation of Fujian Province (No.2024J011210)the High-Level Talent Start-Up Foundation of Xiamen Institute of Technology (No.YKJ23017R)。
文摘Aqueous sodium-ion batteries(ASIBs)have attracted great attention in aqueous batteries due to their merit of high safety.However,the constrained work potential and insufficient chemical stability of anode materials in aqueous electro-lytes hinder the large-scale application of ASIBs.Sodium titanium phosphate,NaTi_(2)(PO_(4))_(3)(NTP),is considered one of the most promising anode materials for ASIBs due to its excellent electrochemical performance and tunable structure.Recently,great achievements have been made in the development of NTP,however,a comprehensive review of existing studies is still lacking.This article firstly introduces the basic properties of NTP and analyzes the existing challenges.Subsequently,it will provide a comprehensive overview of the key strategies related to the design and modification of NTP materials with optimized electrochemical performance.Finally,based on the current research status and practical needs,suggestions,and future perspectives for advancing NTP in practical applications of ASIBs are presented.This review aims to guide the future research trajectory from basic material innovation to industrial applications,thus promoting the large-scale commercializa-tion of ASIBs.
基金partly supported by the National Natural Science Foundation of China(Grant No.52272225).
文摘Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.
基金support from the Major basic research project of Natural Science Foundation of Shandong Province(No.ZR2023ZD12)Singapore National Research Foundation Investigatorship(No.NRFNRFI08-2022-0009)NUS R&G Postdoc Fellowship Program.
文摘Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degradation at high current densities.We address these issues by a“killing two birds with one stone”O_(2)-pressure protocol.It first resolves efficient O_(2) mass transport at high rates..The accelerated reaction kinetics optimizes the composition and growth pathway of discharge products.This protocol secondly achieves protection of Li anodes via densifying corrosion layers on them.Consequently,the battery delivers both ultrahigh discharge capacity(>9,000 mAh g^(-1))at 3,000 mA g^(-1) and excellent cycling stability.Under a dual-strategy effect of high-pressure O_(2) and artificial protection layers,the battery actualizes over 11-fold increase in cycle life of 5,170 h(2,585 cycles).The strategy opens avenues for advancing Li-O_(2) batteries towards practical application and confers the extension to other gas-based batteries.
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
