In electrochemical energy storage systems,the sodium-ion battery is typically integrated in the form of a“cell-module-cluster”,but its cross-scale thermal runaway triggering risk and the propagation mechanism remain...In electrochemical energy storage systems,the sodium-ion battery is typically integrated in the form of a“cell-module-cluster”,but its cross-scale thermal runaway triggering risk and the propagation mechanism remain unclear.This study reveals the cross-scale thermal runaway triggering and propagation behavior of sodium-ion batteries of“cell-module-cluster”under overcharge conditions,and investigates the effects of key factors,including module spacing,triggering cell location,and heat dissipation condition,on the thermal runaway propagation behavior.Results demonstrate that the thermal runaway propagation in a module containing the overcharged cell follows a sequential triggering mode,while thermal runaway in the downstream module exhibits a simultaneous triggering mode with greater severity.Furthermore,increasing the module spacing or enhancing the heat dissipation capacity can effectively reduce the heat accumulation and prevent the trigger of thermal runaway.On the above basis,the multi-dimensional evaluation strategy is proposed to quantitatively assess the hazard of sodium-ion battery cluster thermal runaway.The findings serve as a foundation for the safe design of sodium-ion batteries in energy storage systems.展开更多
Zinc telluride(ZnTe)with high density and low cost is considered as promising anode for sodium-ion batteries.However,ZnTe suffers from continuous capacity degradation owing to the low electronic conductivity,large vol...Zinc telluride(ZnTe)with high density and low cost is considered as promising anode for sodium-ion batteries.However,ZnTe suffers from continuous capacity degradation owing to the low electronic conductivity,large volume expansion,and high ion-diffusion energy barriers.Herein,the nitrogen-doped carbon confined ZnTe polyhedron heterostructure(ZnTe/NC)is proposed,exploiting its orbital rehybridization and the realignment of energy level to improve storage performance.Systematic ex situ/in situ characterizations and simulations demonstrated that the elaborate ZnTe/NC offers abundant electron/ion transport pathways,accelerates Na^(+)diffusion kinetics,and alleviates huge volume expansion.Notably,the nitrogen-doped carbon-support interaction induced via electron transfer between ZnTe sites and support elevates the energy level of Zn 3d orbital,greatly enhancing ion adsorption capability and reducing the ion diffusion barrier.As a result,the ZnTe/NC anode delivers a high discharge capacity of 470.5 mAh g^(−1)and long cycling durability over 1000 cycles.This work uncovers that optimizing sodium ion adsorption and diffusion via d-orbital energy level modulation enabled by nitrogen-doped support interaction is an effective method for developing high-performance transition metal telluride anodes for alkali ion storage.展开更多
The intrinsic insulation and drastic volume change of the red phosphorus during the 3-electron alloying process greatly limits its widespread applications in sodium-ion batteries.Here,we report a monomicelle-directed ...The intrinsic insulation and drastic volume change of the red phosphorus during the 3-electron alloying process greatly limits its widespread applications in sodium-ion batteries.Here,we report a monomicelle-directed assembly approach for controllable synthesis of monodispersed mesoporous polypyrrole(PPy)nanospheres,which allows for the shape-preserving conversion into N-doped carbon with regular mesoscopic pore and high surface area,thus affording a high dispersion of red phosphorus during melt impregnation process due to the available diffusion apertures and strong molecular chemical anchoring.Moreover,the theoretical calculations further revealed that positively polarized pyridine N atoms in N-doped mesoporous carbon nanospheres can empower comprehensive regulation of red phosphorus adsorption by strong chemical binding.Benefitting from the above advantages,the resultant red phosphorus host for sodium-ion batteries delivered an outstanding reversible capacity of 856 mAh/g with a capacity fading rate of only 0.025%per cycle during 1000 cycles at 1.0 A/g.This work provides an effective approach based on monomicelle-directed assembly engineering of carbon-based phosphorus hosts for advanced energy conversion and storage systems.展开更多
Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique ...Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.展开更多
Layered transition metal oxide cathode materials have garnered increasing attention for sodium-ion batteries(SIBs).However,they are plagued by the Jahn-Teller distortion of MnO6,Na^(+)/vacancy ordering,and irreversibl...Layered transition metal oxide cathode materials have garnered increasing attention for sodium-ion batteries(SIBs).However,they are plagued by the Jahn-Teller distortion of MnO6,Na^(+)/vacancy ordering,and irreversible lattice oxygen loss,which collectively lead to capacity fading and voltage decay.Herein,we report a P2-type material,Na_(0.67)Ni_(0.3)Mn_(0.6)Li_(0.09)Sn_(0.01)O_(2)(NNMO-Li0.09Sn0.01),modified with two closed-shell dopants(i.e.,Li^(+)and Sn^(4+)).Benefiting from the unique electronic configurations of closed-shell ions,NNMO-Li0.09Sn0.01 exhibits enhanced structural and electrochemical stability.Specifically,the incorporation of Li^(+)increases the Mn^(4+)/Mn3+ratio,thereby mitigating Jahn-Teller distortion during(de)sodiation process.In addition,Li^(+)disrupts the Ni/Mn ordering in the transition metal layer,suppressing Na^(+)/vacancy ordering.Meanwhile,the introduction of Sn^(4+)forms stronger Sn-O bonds(548 kJ mol-1),thereby enhancing the bonding strength between neighboring transition metal ions and surrounding oxygen atoms,effectively reducing oxygen loss during cycling.NNMO-Li0.09Sn0.01 exhibits significantly improved cycling stability,delivering a specific capacity of 90.3 mAh g^(-1)with 62.9%capacity retention after 50 cycles at 0.1 C(1 C=200 mA g^(-1)),along with 90.3%voltage retention.This substitution strategy based on closed-shell ions offers a viable approach for enhancing the structural stability of wide-voltage layered oxide cathodes.展开更多
The application of conventional manganese dioxide(MnO_(2))materials in sodium-ion supercapacitors(Na-SCs)is considerably limited by their low conductivity and structural instability.Biomimetic morphology engineering c...The application of conventional manganese dioxide(MnO_(2))materials in sodium-ion supercapacitors(Na-SCs)is considerably limited by their low conductivity and structural instability.Biomimetic morphology engineering can optimize the electrochemical performance of MnO_(2).Here,based on the metal-organic frameworks(MOFs)-derived method and electrochemical reconstruction,a coral-like MnO_(2)structure integrated with a functional nitrogen-doped carbon(NC)coating is designed for Na-SC application.The bioinspired coral-like structure captures numerous electrolyte ions and increases the Na+concentration on the electrode surface,which is beneficial for optimizing the Na+transport pathway and accelerating the electrode reaction kinetics.Moreover,the coral-like crosslinked structure effectively enhances the mechanical properties,enabling the maintenance of the structure of MnO_(2)-based electrodes during long-term operation.Furthermore,in/ex-situ characterizations are performed to elucidate the mechanism of lattice transformation during electrochemical phase reconstruction.Additionally,the theoretical calculation and simulation results reveal the ion/electron dynamics in the fabricated electrode.The prepared electrode demonstrates excellent capacitance storage ability(340.7 F g^(−1)at 0.5 A g^(−1))and cycling stability(85.1%capacitance retention after 10,000 cycles).The assembled hybrid device exhibits exceptional life-span(82.0%capacitance retention after 10,000 cycles)and exceptional energy density(36.5 Wh kg^(−1)).This study provides a reliable biomimetic morphology design strategy for MnO_(2)cathodes,paving the way for the fabrication of high-performance Na-SCs.展开更多
The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batte...The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).展开更多
O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe ...O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.展开更多
Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy ...Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.展开更多
Metal phosphides have been studied as prospective anode materials for sodium-ion batteries(SIBs)due to their higher specific capacity compared to other anode materials.However,rapid capacity decay and limited cycle li...Metal phosphides have been studied as prospective anode materials for sodium-ion batteries(SIBs)due to their higher specific capacity compared to other anode materials.However,rapid capacity decay and limited cycle life caused by volume expansion and low electrical conductivity of phosphides in SIBs remain still unsolved.To address these issues,GeP_(3) was first prepared by high-energy ball milling,and then Ketjen black(KB)was introduced to synthesize composite GeP_(3)/KB anode materials under controlled milling speed and time by a secondary ball milling process.During the ball milling process,GeP_(3) and KB form strong chemical bonds,resulting in a closely bonded composite.Consequently,the GeP_(3)/KB anodes was demonstrated excellent sodium storage performance,achieving a high reversible capacity of 933.41 mAh·g^(–1) at a current density of 0.05 A·g^(–1) for a special formula of GeP_(3)/KB-600-40 sample prepared at ball milling speed of 600 r/min for 40 h.Even at a high current density of 2 A·g^(–1) over 200 cycles,the capacity remains 314.52 mAh·g^(–1) with a retention rate of 66.6%.In conclusion,this work successfully prepares GeP_(3)/KB anode-carbon composite for electrodes by high-energy ball milling,which can restrict electrode volume expansion,enhance capacity,and improve cycle stability of SIBs.展开更多
In recent years,sodium-ion batteries(SIBs)have become one of the hot discussions and have gradually moved toward industrialization.However,there are still some shortcomings in their performance that have not been well...In recent years,sodium-ion batteries(SIBs)have become one of the hot discussions and have gradually moved toward industrialization.However,there are still some shortcomings in their performance that have not been well addressed,including phase transition,structural degradation,and voltage platform.High entropy materials have recently gained significant attention from researchers due to their effects on thermodynamics,dynamics,structure,and performance.Researchers have attempted to use these materials in sodium-ion batteries to overcome their problems,making it a modification method.This paper aims to discuss the research status of high-entropy cathode materials for sodium-ion batteries and summarize their effects on sodium-ion batteries from three perspectives:Layered oxide,polyanion,and Prussian blue.The infiuence on material structure,the inhibition of phase transition,and the improvement of ion diffusivity are described.Finally,the advantages and disadvantages of high-entropy cathode materials for sodium-ion batteries are summarized,and their future development has prospected.展开更多
Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electric...Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electrical conductivity.Unlike well-studied graphene,perovskite and MXene materials in various fields,the research about MBene is still in its infancy.The inadequate exploration of efficient etching methods impedes their further study.Herein,we put forward an efficient microwave-assisted hydrother-mal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure,which displays a remarkable electrochemical performance in sodium ion batter-ies(SIBs)with a reversible specific capacity of 196.5 mAh g^(-1)at the current density of 50 mA g^(-1),and 138.6 mAh g^(-1)after 500 cycles at the current density of 0.5 A g^(-1).The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations.This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.展开更多
Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor...Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.展开更多
Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius o...Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.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
The future large-scale application of sodium-ion batteries(SIBs)is inseparable from their excellent electrochemical performance and reliable safety characteristics.At present,there are few studies focusing on their sa...The future large-scale application of sodium-ion batteries(SIBs)is inseparable from their excellent electrochemical performance and reliable safety characteristics.At present,there are few studies focusing on their safety performance.The analysis of thermal stability and structural changes within a single material cannot systematically describe the complex interplay of components within the battery system during the thermal runaway process.Furthermore,the reaction between the battery materials themselves and their counterparts within the system can stimulate more intense exothermic behavior,thereby affecting the safety of the entire battery system.Therefore,this study delved into the thermal generation and gas evolution characteristics of the positive electrode(Na_(x)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2),NFM111)and the negative electrode(hard carbon,HC)in SIBs,utilizing various material combinations.Through the integration of microscopic and macroscopic characterization techniques,the underlying reaction mechanisms of the positive and negative electrode materials within the battery during the heating process were elucidated.Three important results are derived from this study:(Ⅰ)The instability of the solid electrolyte interphase(SEI)leads to its decomposition at temperatures below 100℃,followed by extensive decomposition within the range of 100-150℃,yielding heat and the formation of inorganic compounds,such as Na_(2)CO_(3)and Na_(2)O;(Ⅱ)The reaction between NFM111 and the electrolyte constitutes the primary exothermic event during thermal abuse,with a discernible reaction also occurring between sodium metal and the electrolyte throughout the heating process;(Ⅲ)The heat production and gas generation behaviors of multi-component reactions do not exhibit complete correlation,and the occurrence of gas production does not necessarily coincide with thermal behavior.The results presented in this study can provide useful guidance for the safety improvement of SIBs.展开更多
Cascading thermal runaway(TR)propagation poses a critical safety concern for large-format sodium-ion battery(SIB)systems because of the heightened risks of fires or explosions.However,effectively suppressing TR propag...Cascading thermal runaway(TR)propagation poses a critical safety concern for large-format sodium-ion battery(SIB)systems because of the heightened risks of fires or explosions.However,effectively suppressing TR propagation without introducing unintended side effects remains a significant challenge.Herein,we demonstrate a localized energy release method to mitigate TR,by reducing the state of charge(SOC)of cells adjacent to the thermally runaway unit.We discover that as the SOCs decreased from 100%to 25%,the TR trigger temperature decreased significantly,and the maximum temperature decrease from 367 to 229℃.Meanwhile,the volume of gas decreased to one-third of its original value,while the range of explosion limits significantly narrowed.The analysis of the morphology of the debris further confirms that the structural damage is greater at higher SOC levels.Moreover,an Entropy Weight and Technique for Order Preference by Similarity to an Ideal Solution(EW-TOPSIS)method has been established to assess the safety status of SIBs,showing that the TR possibility is nearly linear with the SOCs,and the TR hazard is exponentially related to the SOCs.Finally,when the SOC of cells adjacent to the TR cell is reduced to 25%,TR can be directly blocked without the need for additional cooling or thermal insulation methods.This study not only advances the understanding of TR behavior in SIBs but also offers a straightforward approach to mitigating the TR risk in SIB systems.展开更多
Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, th...Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, their application is hindered by poor cycling stability, resulting from severe volume changes during cycling and slow reaction kinetics due to their complex crystal structure. Here, an efficient and straightforward strategy was employed to in-situ encapsulate single-phase porous nanocubic MnS_(0.5)Se_(0.5) into carbon nanofibers using electrospinning and the hard template method, thus forming a necklace-like porous MnS_(0.5)Se_(0.5)-carbon nanofiber composite(MnS_(0.5)Se_(0.5)@N-CNF). The introduction of Se significantly impacts both the composition and microstructure of MnS_(0.5)Se_(0.5), including lattice distortion that generates additional defects, optimization of chemical bonds, and a nano-spatially confined design. In situ/ex-situ characterization and density functional theory calculations verified that this MnS_(0.5)Se_(0.5)@N-CNF allevi- ates the volume expansion and facilitates the transfer of Na+/electron. As expected, MnS_(0.5)Se_(0.5)@N-CNF anode demonstrates excellent sodium storage performance, characterized by high initial Coulombic efficiency(90.8%), high-rate capability(370.5 m Ahg^(-1) at 10 Ag^(-1)) and long durability(over 5000 cycles at 5 Ag^(-1)). The MnS_(0.5)Se_(0.5)@N-CNF//NVP@C full cell, assembled with MnS_(0.5)Se_(0.5)@N-CNF as anode and Na_(3)V_(2)(PO_4)_(3)@C as cathode, exhibits a high energy density of 254 Wh kg^(-1) can be provided. This work presents a novel strategy to optimize the design of anode materials through structural engineering and Se substitution, while also elucidating the underlying reaction mechanisms.展开更多
Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials ...Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.展开更多
Complex phase transitions occur in P2-type materials during charging and discharging.A high-entropy structure can effectively inhibit the structural phase transition of a P2-type layered material.In this study,a hight...Complex phase transitions occur in P2-type materials during charging and discharging.A high-entropy structure can effectively inhibit the structural phase transition of a P2-type layered material.In this study,a hightemperature solid-phase method is used to synthesize the P2-type high-entropy fluorine oxide(HEFO)Na_(0.7)Li_(0.08)Mn(Ⅳ)_(0.21)Mn(Ⅲ)_(0.43)Mg_(0.11)Ni_(0.11)W_(0.04)Nb_(0.02)O_(1.9)F_(0.1)[■-NLM(Ⅳ)0.21M(Ⅲ)0.43F(■=NMNWO)],with a superlattice structure and Na_(2)WO_(4)coating.Na_(2)WO_(4)can effectively inhibit the complex phase transition to improve the structural stability of the material and overcome the limitations of P2-type Na_(x)TMO_(2)(TM=transition metal)via additional charge compensation.Adjusting the Mn^(3+)/Mn^(4+)ratio to increase the average valence state of Mn and introducing F^(-)and Li^(+)to inhibit the Jahn-Teller effect suppress the complex phase transition during charging and discharging.The material exhibits a good multiplicative performance(discharge specific capacity of 88.4 mAh g^(-1)at a multiplicative rate of 10C)and capacity retention(99.22%after 200 cycles at 1C in the potential window of 1.5-4.3 V).The structural stabilities of HEFO are effectively demonstrated using electrochemical in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy.Theoretical calculations reveal that the high-entropy structure effectively improves the electronic structure and charge distribution of the layered oxide material.This study provides new concepts for use in developing novel energy batteries.展开更多
基金supported by the Anhui Quality Infrastructure Standardization Project(Grant No.2024MKSO7)the Science and Technology Project of State Grid(SGAHDK00DJJS2310027)the Anhui Provincial Natural Science Foundation(Grant No.2208085UD03).
文摘In electrochemical energy storage systems,the sodium-ion battery is typically integrated in the form of a“cell-module-cluster”,but its cross-scale thermal runaway triggering risk and the propagation mechanism remain unclear.This study reveals the cross-scale thermal runaway triggering and propagation behavior of sodium-ion batteries of“cell-module-cluster”under overcharge conditions,and investigates the effects of key factors,including module spacing,triggering cell location,and heat dissipation condition,on the thermal runaway propagation behavior.Results demonstrate that the thermal runaway propagation in a module containing the overcharged cell follows a sequential triggering mode,while thermal runaway in the downstream module exhibits a simultaneous triggering mode with greater severity.Furthermore,increasing the module spacing or enhancing the heat dissipation capacity can effectively reduce the heat accumulation and prevent the trigger of thermal runaway.On the above basis,the multi-dimensional evaluation strategy is proposed to quantitatively assess the hazard of sodium-ion battery cluster thermal runaway.The findings serve as a foundation for the safe design of sodium-ion batteries in energy storage systems.
基金supported by the National Natural Science Foundation of China(52402298,52172224,52302240)Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)+1 种基金the Macao Young Scholars Program(AM2023011)the Yuanguang Scholars Program,Hebei University of Technology(282022554).
文摘Zinc telluride(ZnTe)with high density and low cost is considered as promising anode for sodium-ion batteries.However,ZnTe suffers from continuous capacity degradation owing to the low electronic conductivity,large volume expansion,and high ion-diffusion energy barriers.Herein,the nitrogen-doped carbon confined ZnTe polyhedron heterostructure(ZnTe/NC)is proposed,exploiting its orbital rehybridization and the realignment of energy level to improve storage performance.Systematic ex situ/in situ characterizations and simulations demonstrated that the elaborate ZnTe/NC offers abundant electron/ion transport pathways,accelerates Na^(+)diffusion kinetics,and alleviates huge volume expansion.Notably,the nitrogen-doped carbon-support interaction induced via electron transfer between ZnTe sites and support elevates the energy level of Zn 3d orbital,greatly enhancing ion adsorption capability and reducing the ion diffusion barrier.As a result,the ZnTe/NC anode delivers a high discharge capacity of 470.5 mAh g^(−1)and long cycling durability over 1000 cycles.This work uncovers that optimizing sodium ion adsorption and diffusion via d-orbital energy level modulation enabled by nitrogen-doped support interaction is an effective method for developing high-performance transition metal telluride anodes for alkali ion storage.
基金supported by the National Natural Science Foundation of China(Nos.52373208 and 61831021)the Shanghai Undergraduate Training Program on Innovation and Entrepreneurship(No.202310269131S).
文摘The intrinsic insulation and drastic volume change of the red phosphorus during the 3-electron alloying process greatly limits its widespread applications in sodium-ion batteries.Here,we report a monomicelle-directed assembly approach for controllable synthesis of monodispersed mesoporous polypyrrole(PPy)nanospheres,which allows for the shape-preserving conversion into N-doped carbon with regular mesoscopic pore and high surface area,thus affording a high dispersion of red phosphorus during melt impregnation process due to the available diffusion apertures and strong molecular chemical anchoring.Moreover,the theoretical calculations further revealed that positively polarized pyridine N atoms in N-doped mesoporous carbon nanospheres can empower comprehensive regulation of red phosphorus adsorption by strong chemical binding.Benefitting from the above advantages,the resultant red phosphorus host for sodium-ion batteries delivered an outstanding reversible capacity of 856 mAh/g with a capacity fading rate of only 0.025%per cycle during 1000 cycles at 1.0 A/g.This work provides an effective approach based on monomicelle-directed assembly engineering of carbon-based phosphorus hosts for advanced energy conversion and storage systems.
基金supported by the National Nature Science Foundation of China(Nos.52202335 and 52171227)Natural Science Foundation of Jiangsu Province(No.BK20221137)National Key R&D Program of China(2024YFE0108500).
文摘Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.
基金supported by the Ministry of Science and Technology of China(2025YFE0100200)the Natural Science Foundation of Tianjin(24JCJQJC00220 and 24ZXZSSS00310)+3 种基金the National Natural Science Foundation of China(22479080,92372203,and 92372001)the Open Foundation of Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(JDSX2023003)the Fundamental Research Funds for the Central Universities of Nankai University(020-63253167)the"111 Center"(B25010)。
文摘Layered transition metal oxide cathode materials have garnered increasing attention for sodium-ion batteries(SIBs).However,they are plagued by the Jahn-Teller distortion of MnO6,Na^(+)/vacancy ordering,and irreversible lattice oxygen loss,which collectively lead to capacity fading and voltage decay.Herein,we report a P2-type material,Na_(0.67)Ni_(0.3)Mn_(0.6)Li_(0.09)Sn_(0.01)O_(2)(NNMO-Li0.09Sn0.01),modified with two closed-shell dopants(i.e.,Li^(+)and Sn^(4+)).Benefiting from the unique electronic configurations of closed-shell ions,NNMO-Li0.09Sn0.01 exhibits enhanced structural and electrochemical stability.Specifically,the incorporation of Li^(+)increases the Mn^(4+)/Mn3+ratio,thereby mitigating Jahn-Teller distortion during(de)sodiation process.In addition,Li^(+)disrupts the Ni/Mn ordering in the transition metal layer,suppressing Na^(+)/vacancy ordering.Meanwhile,the introduction of Sn^(4+)forms stronger Sn-O bonds(548 kJ mol-1),thereby enhancing the bonding strength between neighboring transition metal ions and surrounding oxygen atoms,effectively reducing oxygen loss during cycling.NNMO-Li0.09Sn0.01 exhibits significantly improved cycling stability,delivering a specific capacity of 90.3 mAh g^(-1)with 62.9%capacity retention after 50 cycles at 0.1 C(1 C=200 mA g^(-1)),along with 90.3%voltage retention.This substitution strategy based on closed-shell ions offers a viable approach for enhancing the structural stability of wide-voltage layered oxide cathodes.
基金supported by the National Natural Science Foundation of China(22409065)the Guangdong Basic and Applied Basic Research Foundation(2022A1515011906)+2 种基金the China Postdoctoral Science Foundation(2023M731153)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technologythe Postdoctoral Fellowship Program of CPSF(GZC20230868).
文摘The application of conventional manganese dioxide(MnO_(2))materials in sodium-ion supercapacitors(Na-SCs)is considerably limited by their low conductivity and structural instability.Biomimetic morphology engineering can optimize the electrochemical performance of MnO_(2).Here,based on the metal-organic frameworks(MOFs)-derived method and electrochemical reconstruction,a coral-like MnO_(2)structure integrated with a functional nitrogen-doped carbon(NC)coating is designed for Na-SC application.The bioinspired coral-like structure captures numerous electrolyte ions and increases the Na+concentration on the electrode surface,which is beneficial for optimizing the Na+transport pathway and accelerating the electrode reaction kinetics.Moreover,the coral-like crosslinked structure effectively enhances the mechanical properties,enabling the maintenance of the structure of MnO_(2)-based electrodes during long-term operation.Furthermore,in/ex-situ characterizations are performed to elucidate the mechanism of lattice transformation during electrochemical phase reconstruction.Additionally,the theoretical calculation and simulation results reveal the ion/electron dynamics in the fabricated electrode.The prepared electrode demonstrates excellent capacitance storage ability(340.7 F g^(−1)at 0.5 A g^(−1))and cycling stability(85.1%capacitance retention after 10,000 cycles).The assembled hybrid device exhibits exceptional life-span(82.0%capacitance retention after 10,000 cycles)and exceptional energy density(36.5 Wh kg^(−1)).This study provides a reliable biomimetic morphology design strategy for MnO_(2)cathodes,paving the way for the fabrication of high-performance Na-SCs.
基金supported by the Low-Cost Long-Life Batteries program,China(No.WL-24-08-01)the National Natural Science Foundation of China(No.22279007)。
文摘The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).
基金supported by the National Natural Science Foundation of China (52402298, 52172224, 52202228, 22479112)the Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)+3 种基金Science Research Project of Hebei Education Department (BJK2022011)Central Funds Guiding the Local Science and Technology Development of Hebei Province (236Z4404G)the Beijing Tianjin Hebei Basic Research Cooperation Special Project(E2024202273)Tianjin Sci.&Tech. Program (22YFYSHZ00220)
文摘O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52573299)the Natural Science Foundation of Jiangxi province(No.20242BAB25223,20232BCJ23025,20232BCJ25040,20232BAB214024)the Special Funding Program for Graduate Student Innovation of Jiangxi Province(No.YC2024-S594).
文摘Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.
基金National Natural Science Foundation of China Young Scientist Fund(22105120)Shaanxi Province Qin Chuangyuan“Scientist+Engineer”Team Construction Project(2024QCY-KXJ-127)。
文摘Metal phosphides have been studied as prospective anode materials for sodium-ion batteries(SIBs)due to their higher specific capacity compared to other anode materials.However,rapid capacity decay and limited cycle life caused by volume expansion and low electrical conductivity of phosphides in SIBs remain still unsolved.To address these issues,GeP_(3) was first prepared by high-energy ball milling,and then Ketjen black(KB)was introduced to synthesize composite GeP_(3)/KB anode materials under controlled milling speed and time by a secondary ball milling process.During the ball milling process,GeP_(3) and KB form strong chemical bonds,resulting in a closely bonded composite.Consequently,the GeP_(3)/KB anodes was demonstrated excellent sodium storage performance,achieving a high reversible capacity of 933.41 mAh·g^(–1) at a current density of 0.05 A·g^(–1) for a special formula of GeP_(3)/KB-600-40 sample prepared at ball milling speed of 600 r/min for 40 h.Even at a high current density of 2 A·g^(–1) over 200 cycles,the capacity remains 314.52 mAh·g^(–1) with a retention rate of 66.6%.In conclusion,this work successfully prepares GeP_(3)/KB anode-carbon composite for electrodes by high-energy ball milling,which can restrict electrode volume expansion,enhance capacity,and improve cycle stability of SIBs.
基金the National Natural Science Foundation of China Key Program(No.U22A20420)Changzhou Leading Innovative Talents Introduction and Cultivation Project(No.CQ20230109)for supporting our work。
文摘In recent years,sodium-ion batteries(SIBs)have become one of the hot discussions and have gradually moved toward industrialization.However,there are still some shortcomings in their performance that have not been well addressed,including phase transition,structural degradation,and voltage platform.High entropy materials have recently gained significant attention from researchers due to their effects on thermodynamics,dynamics,structure,and performance.Researchers have attempted to use these materials in sodium-ion batteries to overcome their problems,making it a modification method.This paper aims to discuss the research status of high-entropy cathode materials for sodium-ion batteries and summarize their effects on sodium-ion batteries from three perspectives:Layered oxide,polyanion,and Prussian blue.The infiuence on material structure,the inhibition of phase transition,and the improvement of ion diffusivity are described.Finally,the advantages and disadvantages of high-entropy cathode materials for sodium-ion batteries are summarized,and their future development has prospected.
基金supported by the National Key Re-search and Development Program of China(No.2020YFC1909604)SZIIT Startup Fund(No.SZIIT2022KJ072)+1 种基金Shenzhen Peacock Project Startup Fund(No.RC2023-002)Shenzhen Steady General Projects(No.KJ2024C010).
文摘Two-dimensional(2D)transition metal borides(MBenes)have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and ex-cellent electrical conductivity.Unlike well-studied graphene,perovskite and MXene materials in various fields,the research about MBene is still in its infancy.The inadequate exploration of efficient etching methods impedes their further study.Herein,we put forward an efficient microwave-assisted hydrother-mal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure,which displays a remarkable electrochemical performance in sodium ion batter-ies(SIBs)with a reversible specific capacity of 196.5 mAh g^(-1)at the current density of 50 mA g^(-1),and 138.6 mAh g^(-1)after 500 cycles at the current density of 0.5 A g^(-1).The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations.This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.
基金supported by the National Natural Science Foundation of China(22209103)Science and Technology Commission of Shanghai Municipality(22010500400)Australian Research Council(FT180100705)。
文摘Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.
基金financially supported by the Natural Science Foundation of China(Nos.22208214,22005190,and 21938005)the Science&Technology Commission of Shanghai Municipality(Nos.20QB1405700,and 19DZ1205500)Zhejiang Key Research and Development Program(No.2020C01128)
文摘Sodium-ion batteries(SIBs) are promising electrochemical energy storage systems as lithium-ion batteries by virtue of their similar chemical properties and natural abundance and availability.However,the ionic radius of Na^(+)is larger than that of Li^(+),leading to challenges in its insertion/extraction at anode side.As a class of anode materials,phosphorus allotropes(PAs,red,and black) and metal phosphides(MPs) have shown great prospects because of high theoretical gravimetric/volumetric capacity,high carrier mobility,and suitable redox potential.In this review,recent developments in the studies of PAs and MPs with particular emphasis on understanding sodium storage mechanisms,developing novel synthesis strategies,and performance validations have been manifested valuable solutions to address these challenges.We begin with the introduction and classification of the macroscopic sodiation mechanisms of PAs and MPs,and the various fabrication strategies of PAs and MPs are comprehensively summarized in second section.The third section thoroughly reviews the progresses on PAs and MPs-based advanced materials for their application in SIBs.Finally,we also discuss the significant challenges and outline a roadmap for future research directions.
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 National Natural Science Foundation of China(52404259)supported by Youth Innovation Promotion Association CAS(Y201768)。
文摘The future large-scale application of sodium-ion batteries(SIBs)is inseparable from their excellent electrochemical performance and reliable safety characteristics.At present,there are few studies focusing on their safety performance.The analysis of thermal stability and structural changes within a single material cannot systematically describe the complex interplay of components within the battery system during the thermal runaway process.Furthermore,the reaction between the battery materials themselves and their counterparts within the system can stimulate more intense exothermic behavior,thereby affecting the safety of the entire battery system.Therefore,this study delved into the thermal generation and gas evolution characteristics of the positive electrode(Na_(x)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2),NFM111)and the negative electrode(hard carbon,HC)in SIBs,utilizing various material combinations.Through the integration of microscopic and macroscopic characterization techniques,the underlying reaction mechanisms of the positive and negative electrode materials within the battery during the heating process were elucidated.Three important results are derived from this study:(Ⅰ)The instability of the solid electrolyte interphase(SEI)leads to its decomposition at temperatures below 100℃,followed by extensive decomposition within the range of 100-150℃,yielding heat and the formation of inorganic compounds,such as Na_(2)CO_(3)and Na_(2)O;(Ⅱ)The reaction between NFM111 and the electrolyte constitutes the primary exothermic event during thermal abuse,with a discernible reaction also occurring between sodium metal and the electrolyte throughout the heating process;(Ⅲ)The heat production and gas generation behaviors of multi-component reactions do not exhibit complete correlation,and the occurrence of gas production does not necessarily coincide with thermal behavior.The results presented in this study can provide useful guidance for the safety improvement of SIBs.
基金supported by the National Key R&D Program of China(2023YFB2407900)the National Natural Science Foundation of China(52302512)+1 种基金State Key Laboratory of New Ceramic and Fine Processing Tsinghua University(KFZD202305)Zhejiang Province Science and Technology Program Grant(2024C0127(SD2))。
文摘Cascading thermal runaway(TR)propagation poses a critical safety concern for large-format sodium-ion battery(SIB)systems because of the heightened risks of fires or explosions.However,effectively suppressing TR propagation without introducing unintended side effects remains a significant challenge.Herein,we demonstrate a localized energy release method to mitigate TR,by reducing the state of charge(SOC)of cells adjacent to the thermally runaway unit.We discover that as the SOCs decreased from 100%to 25%,the TR trigger temperature decreased significantly,and the maximum temperature decrease from 367 to 229℃.Meanwhile,the volume of gas decreased to one-third of its original value,while the range of explosion limits significantly narrowed.The analysis of the morphology of the debris further confirms that the structural damage is greater at higher SOC levels.Moreover,an Entropy Weight and Technique for Order Preference by Similarity to an Ideal Solution(EW-TOPSIS)method has been established to assess the safety status of SIBs,showing that the TR possibility is nearly linear with the SOCs,and the TR hazard is exponentially related to the SOCs.Finally,when the SOC of cells adjacent to the TR cell is reduced to 25%,TR can be directly blocked without the need for additional cooling or thermal insulation methods.This study not only advances the understanding of TR behavior in SIBs but also offers a straightforward approach to mitigating the TR risk in SIB systems.
基金financially supported by the National Natural Science Foundation of China (No. 22225902, U22A20436, 22209185)National Key Research&Development Program of China (2022YFE0115900, 2023YFA1507101, 2021YFA1501500)+1 种基金the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences (No. CXZX-2022-GH04, CXZX-2023-JQ08)Science and Technology Program of Fuzhou (2023-P-009)。
文摘Manganese-based chalcogenides have significant potential as anodes for sodium-ion batteries(SIBs) due to their high theoretical specific capacity, abundant natural reserves, and environmental friendliness. However, their application is hindered by poor cycling stability, resulting from severe volume changes during cycling and slow reaction kinetics due to their complex crystal structure. Here, an efficient and straightforward strategy was employed to in-situ encapsulate single-phase porous nanocubic MnS_(0.5)Se_(0.5) into carbon nanofibers using electrospinning and the hard template method, thus forming a necklace-like porous MnS_(0.5)Se_(0.5)-carbon nanofiber composite(MnS_(0.5)Se_(0.5)@N-CNF). The introduction of Se significantly impacts both the composition and microstructure of MnS_(0.5)Se_(0.5), including lattice distortion that generates additional defects, optimization of chemical bonds, and a nano-spatially confined design. In situ/ex-situ characterization and density functional theory calculations verified that this MnS_(0.5)Se_(0.5)@N-CNF allevi- ates the volume expansion and facilitates the transfer of Na+/electron. As expected, MnS_(0.5)Se_(0.5)@N-CNF anode demonstrates excellent sodium storage performance, characterized by high initial Coulombic efficiency(90.8%), high-rate capability(370.5 m Ahg^(-1) at 10 Ag^(-1)) and long durability(over 5000 cycles at 5 Ag^(-1)). The MnS_(0.5)Se_(0.5)@N-CNF//NVP@C full cell, assembled with MnS_(0.5)Se_(0.5)@N-CNF as anode and Na_(3)V_(2)(PO_4)_(3)@C as cathode, exhibits a high energy density of 254 Wh kg^(-1) can be provided. This work presents a novel strategy to optimize the design of anode materials through structural engineering and Se substitution, while also elucidating the underlying reaction mechanisms.
基金National Key Research and Development Program of China (2022YFB2402200)National Natural Science Foundation of China (22225201,22379028)+2 种基金Fundamental Research Funds for the Central Universities (20720220010)Shanghai Pilot Program for Basic Research–Fudan University 21TQ1400100 (21TQ009)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (23520750400)。
文摘Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.
基金financially supported by the Guizhou Provincial Basic Research Program(Natural Science)(No.QKHJC-ZK[2023]YB051)the Natural Science Special Foundation of Guizhou University(No.GDTGH[2022]33)+2 种基金the Natural Science Research project of the Education Department of Guizhou Province(No.QJJ[2022]001)the National Natural Science Foundation of China(No.52161029)the Science and Technology Innovation Team of Education Agency in Guizhou Province(No.Qian Jiao Ji[2023]056)
文摘Complex phase transitions occur in P2-type materials during charging and discharging.A high-entropy structure can effectively inhibit the structural phase transition of a P2-type layered material.In this study,a hightemperature solid-phase method is used to synthesize the P2-type high-entropy fluorine oxide(HEFO)Na_(0.7)Li_(0.08)Mn(Ⅳ)_(0.21)Mn(Ⅲ)_(0.43)Mg_(0.11)Ni_(0.11)W_(0.04)Nb_(0.02)O_(1.9)F_(0.1)[■-NLM(Ⅳ)0.21M(Ⅲ)0.43F(■=NMNWO)],with a superlattice structure and Na_(2)WO_(4)coating.Na_(2)WO_(4)can effectively inhibit the complex phase transition to improve the structural stability of the material and overcome the limitations of P2-type Na_(x)TMO_(2)(TM=transition metal)via additional charge compensation.Adjusting the Mn^(3+)/Mn^(4+)ratio to increase the average valence state of Mn and introducing F^(-)and Li^(+)to inhibit the Jahn-Teller effect suppress the complex phase transition during charging and discharging.The material exhibits a good multiplicative performance(discharge specific capacity of 88.4 mAh g^(-1)at a multiplicative rate of 10C)and capacity retention(99.22%after 200 cycles at 1C in the potential window of 1.5-4.3 V).The structural stabilities of HEFO are effectively demonstrated using electrochemical in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy.Theoretical calculations reveal that the high-entropy structure effectively improves the electronic structure and charge distribution of the layered oxide material.This study provides new concepts for use in developing novel energy batteries.
