High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs ...High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.展开更多
Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted b...Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.展开更多
The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of thes...The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.展开更多
Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising a...Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising as SIBs cathodes due to their high theoretical capacities and facile synthesis.However,their practical applications are hindered by the limitations in energy density and cycling stability.The comprehensive understanding of failure mechanisms within bulk structure and at the cathode/electrolyte interface of cathodes is still lacking.In this review,the issues related to bulk phase degradation and surface degradation,such as irreversible phase transitions,cation migration,transition metal dissolution,air/moisture instability,intergranular cracking,interfacial reactions,and reactive oxygen loss,are discussed.The latest advances and strategies to improve the stability of layered oxide cathodes and full cells are provided,as well as our perspectives on the future development of SIBs.展开更多
Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the ...Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the Jahn-Teller(JT)effect associated with Mn-ion,the cathode exhibits poor structural stability.Herein,we propose a strategy to enhance structural stability by introducing robust metal-oxygen(M-O)bonds,which can realize the pinning effect to constrain the distortion in the transition metal(TM)layer.Concurrently,all the elements employed have exceptionally high crustal abundance.As a proof of concept,the designed K_(0.5)Mn_(0.9)Mg_(0.025)Ti_(0.025)Al_(0.05)O_(2)cathode exhibited a discharge capacity of approximately 100 mA h g^(-1)at 20 mA g^(-1)with 79%capacity retention over 50 cycles,and 73%capacity retention over 200 cycles at 200 mA g^(-1),showcased much better battery performance than the designed cathode with less robust M-O bonds.The properties of the formed M-O bonds were investigated using theoretical calculations.The enhanced dynamics,mitigated JT effect,and improved structural stability were elucidated through the in-situ X-ray diffractometer(XRD),in-situ electrochemical impedance spectroscopy(EIS)(and distribution of relaxation times(DRT)method),and ex-situ X-ray absorption fine structure(XAFS)tests.This study holds substantial reference value for the future design of costeffective Mn-based layered cathodes for PIBs.展开更多
Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cath...Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cathode materials influence the cost and energy output of SIBs.Therefore,the development of advanced cathode materials is crucial for the practical application of SIBs.Among various cathode materials,layered transition metal oxides(LTMOs)have received widespread attention owing to their straightforward preparation,abundant availability,and cost-competitiveness.Notably,layered Fe-based oxide cathodes are deemed to be one of the most promising candidates for the lowest price and easy-to-improve performance.Nevertheless,the challenges such as severe phase transitions,sluggish diffusion kinetics and interfacial degradation pose significant hurdles in achieving high-performance cathodes for SIBs.This review first briefly outlines the classification of layered structures and the working principle of layered oxides.Then,recent advances in modification strategies employed to address current issues with layered iron-based oxide cathodes are systematically reviewed,including ion doping,biphasic engineering and surface modification.Furthermore,the review not only outlines the prospects and development directions for layered Fe-based oxide cathodes but also provides novel insights and directions for future research endeavors for SIBs.展开更多
P2-type layered oxide Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)(NM)is a promising cathode material for sodium-ion batteries(SIBs).However,the severe irreversible phase transition,sluggish Na+diffusion kinetics,and interfacial sid...P2-type layered oxide Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)(NM)is a promising cathode material for sodium-ion batteries(SIBs).However,the severe irreversible phase transition,sluggish Na+diffusion kinetics,and interfacial side reactions at high-voltage result in grievous capacity degradation and inferior electrochemical performance.Herein,a dual-function strategy of entropy tuning and artificial cathode electrolyte interface(CEI)layer construction is reported to generate a novel P2-type medium-entropy Na_(0.75)Li_(0.1)Mg_(0.05)Ni_(0.18)Mn_(0.66)Ta_(0.01)O_(2)with NaTaO_(3)surface modification(LMNMT)to address the aforementioned issues.In situ X-ray diffraction reveals that LMNMT exhibits a near zero-strain phase transition with a volume change of only 1.4%,which is significantly lower than that of NM(20.9%),indicating that entropy tuning effectively suppresses irreversible phase transitions and enhances ion diffusion.Kinetic analysis and post-cycling interfacial characterization further confirm that the artificial CEI layer promotes the formation of a stable,thin NaF-rich CEI and reduces interfacial side reactions,thereby further enhancing ion transport kinetics and surface/interface stability.Consequently,the LMNMT electrode exhibits outstanding rate capability(46 mA h g^(−1)at 20 C)and cycling stability(89.5%capacity retention after 200 cycles at 2 C)within the voltage range of 2–4.35 V.The LMNMT also exhibits superior all-climate performance and air stability.This study provides a novel path for the design of high-voltage cathode materials for SIBs.展开更多
All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for t...All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.展开更多
Ni-rich layered oxide cathode materials such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)face poor interfacial stability and serious side reactions with sulfide solid-state electrolytes.This problem is thought to be exa...Ni-rich layered oxide cathode materials such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)face poor interfacial stability and serious side reactions with sulfide solid-state electrolytes.This problem is thought to be exacerbated by the gradually accumulated basicity of the surface with the Ni content increasing.Herein,the acidic Li_(3)PO_(4)coating layer on NCM811 particles is introduced by ball-milling approach to neutralize the basicity and aggrandize the interfacial stability.The tailored surface structure and components of NCM811 not only suppress the direct contact of cathode particles with sulfide solid-state electrolyte,but also facilitate electrochemical dynamics by driving the Li+migration across the interface and promoting the electron exchange.Thus,cells with Li_(3)PO_(4)coating layer yield 101.3 mAh g^(-1)specific capacity at 2.0 C and highly reversed discharging capacity after suffering from harsh work conditions.Additionally,the stable coating layer broadens the electrochemical windows of cells,delivering long cycle stability(>100 cycles 0.5 C).This contribution highlights the importance of basicity regulation of Ni-rich layered oxide cathode and offers a low-cost and effective approach to design the interfacial structures for the development of all solid-state batteries.展开更多
Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at h...Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at high voltage.In this work,the strategy of the electron donor was utilized to address this issue.Remarkably,the earth-abundant P2-layered cathode Na_(2/3)Al_(1/6)Fe_(1/6)Mn_(2/3)O_(2)with the presence of K_(2)S renders superior rate capability(187.4 and 79.5 mA h g^(-1)at 20 and 1000 mA g^(-1))and cycling stability(a capacity retention of 85.6% over 300 cycles at 1000 mA g^(-1))within the voltage region of 2-4.4 V Na^(+)/Na.Furthermore,excellent electrochemical performance is also demonstrated in the full cell.Detailed structural analysis of as-proposed composite cathode illustrates that even at 4.4 V irreversible phase transition can be avoided as well as a cell volume variation of only 0.88%,which are attributed to the enhanced performance compared with the control group.Meanwhile,further investigation of charge compensation reveals the crucial role of sulfur ions in actively control of reversible redox reaction of oxygen species in the lattice structure.This work inspires a new strategy to enhance the structural stability of layered sodium ion cathode materials at high voltages.展开更多
O3-type layered oxide cathodes for sodium-ion batteries are promising owing to high theoretical capacity and broad temperature adaptability,yet hindered by structural degradation and sluggish Na^(+)diffusion kinetics....O3-type layered oxide cathodes for sodium-ion batteries are promising owing to high theoretical capacity and broad temperature adaptability,yet hindered by structural degradation and sluggish Na^(+)diffusion kinetics.Herein,we present a sodium-deficient high-entropy layered oxide cathode(Na_(0.85)Ni_(0.3)Mn_(0.3)Fe_(0.1)Co_(0.15)Ti_(0.1)Cu_(0.05)B_(0.02)O_(2),denoted as Na0.85-HEO),combining sodium content optimization and high-entropy composition design.Incorporating six transition metals and light element boron creates a unique high-entropy configuration,effectively mitigating local lattice distortion and internal strain through chemical disorder effects,thereby enabling highly reversible phase transitions(O3-P3-O3)and smaller volume change(0.6A^(3))during the initial cycle.The sodium-deficient high-entropy design effectively increases the sodium interlayer spacing to 0.322 nm,facilitating the Na^(+)diffusion kinetics.Moreover,this high-entropy strategy enables the cathode to have a completely solid solution charge curve and significantly reduces the proportion of(O_(2))^(n-),thereby suppressing gas release during the cycling process.The resultant cathode demonstrates exceptional cyclability(80% capacity retention after 400 cycles at 100 mA g^(-1)in a full cell),and remarkable low-temperature performance(108.6 mAh g^(-1)at -40℃).This work guides the design of high-entropy electrode materials with tailored ionic transport channels for extreme-temperature energy storage applications.展开更多
In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-ba...In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.展开更多
Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instabilit...Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.展开更多
In advantages of their high capacity and high operating voltage,the nickel(Ni)-rich layered transition metal oxide cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2)(NCMxyz,x+y+z=1,x≥0.5)and LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2...In advantages of their high capacity and high operating voltage,the nickel(Ni)-rich layered transition metal oxide cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2)(NCMxyz,x+y+z=1,x≥0.5)and LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA))have been arousing great interests to improve the energy density of LIBs.However,these Nirich cathodes always suffer from rapid capacity degradation induced by unstable cathode-electrolyte interphase(CEI)layer and destruction of bulk crystal structure.Therefore,varied electrode/electrolyte interface engineering strategies(such as electrolyte formulation,material coating or doping)have been developed for Ni-rich cathodes protection.Among them,developing electrolyte functional additives has been proven to be a simple,effective,and economic method to improve the cycling stability of Nirich cathodes.This is achieved by removing unfavorable species(such as HF,H_(2)O)or constructing a stable and protective CEI layer against unfavorable reactive species(such as HF,H_(2)O).Herein,this review mainly introduces the varied classes of electrolyte functional additives and their working mechanism for interfacial engineering of Ni-rich cathodes.Especially,key favorable species for stabilizing CEI layer are summarized.More importantly,we put forward perspectives for screening and customizing ideal functional additives for high performance Ni-rich cathodes based LIBs.展开更多
The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/elec...The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/electrochemical side reactions are considered to be the origin of the interfacial deterioration.However,the influence of chemical and electrochemical side reactions on the interfacial deterioration is rarely studied specifically.In this work,the deterioration mechanism of the interface between LiNi0.85-xCo0.15AlxO2 and Li10GeP2S12 is investigated in detail by combining in/ex-situ Raman spectra and Electrochemical Impedance Spectroscopy(EIS).It can be determined that chemical side reaction between LiNi0.8Co0.15Al0.05O2 and Li10GeP2S12 will occur immediately once contacted,and the interfacial deterioration becomes more serious after charge-discharge process under the dual effects of chemical and electrochemical side reactions.Moreover,our research reveals that the interfacial stability and the cycle performance of ASSLB can be greatly enhanced by increasing Al-substitution for Ni in LiNi0.85-xCo0.15AlxO2.In particular,the capacity retention of LiNi0.6Co0.15Al0.25O2 cathode after 200 cycles can reach 81.9%,much higher than that of LiNi0.8Co0.15Al0.05O2 cathode(12.5%@200 cycles).This work gives an insight to study the interfacial issues between Ni-rich layered oxide cathode and sulfide electrolyte for ASSLBs.展开更多
The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by ...The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.展开更多
A novel emissive probe consisting of an oxide cathode coating is developed to achieve a low operating temperature and long service life.The properties of the novel emissive probe are investigated in detail,in comparis...A novel emissive probe consisting of an oxide cathode coating is developed to achieve a low operating temperature and long service life.The properties of the novel emissive probe are investigated in detail,in comparison with a traditional tungsten emissive probe,including the operating temperature,the electron emission capability and the plasma potential measurement.Studies of the operating temperature and electron emission capability show that the tungsten emissive probe usually works at a temperature of 1800 K-2200 K while the oxide cathode emissive probe can function at about 1200 K-1400 K.In addition,plasma potential measurements using the oxide cathode emissive probe with different techniques have been accomplished in microwave electron cyclotron resonance plasmas with different discharge powers.It is found that a reliable plasma potential can be obtained using the improved inflection point method and the hot probe with zero emission limit method,while the floating point method is invalid for the oxide cathode emissive probe.展开更多
Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extracti...Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.展开更多
Li and Mn rich(LMR)layered oxides,written as xLi_(2) MnO_(3)·(1-x)LiMO_(2)(M=Mn,Ni,Co,Fe,etc.),have been widely reported in recent years due to their high capacity and high energy density.The stable structure and...Li and Mn rich(LMR)layered oxides,written as xLi_(2) MnO_(3)·(1-x)LiMO_(2)(M=Mn,Ni,Co,Fe,etc.),have been widely reported in recent years due to their high capacity and high energy density.The stable structure and superior performance of LMR oxides make them one of the most promising candidates for the next-generation cathode materials.However,the commercialization of these materials is hindered by several drawbacks,such as low initial Coulombic efficiency,the degradation of voltage and capacity during cycling,and poor rate performance.This review summarizes research progress in solving these concerns of LMR cathodes over the past decade by following three classes of strategies:morphology design,bulk design,and surface modification.We elaborate on the processing procedures,electrochemical performance,mechanisms,and limitations of each approach,and finally put forward the concerns left and the possible solutions for the commercialization of LMR cathodes.展开更多
Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instabi...Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium-rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium-rich oxide phase transformation and established a clear correlation between the successive consumption of Li+on anode due to incessant interphase repairing and the over-delithiation of lithium-rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium-rich oxide cathode, leading to high capacity and cycling stability.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52202282,52402054,22471283,and 52202327)Natural Science Foundation of Tianjin City(Grant Nos.22JCYBJC00040,24JCQNJC00970)。
文摘High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.
基金supported by the National Key R&D Program of China(2023YFB2406000)the National Natural Science Foundation of China(22479057,52172201,51732005)。
文摘Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.
基金financially supported by the National Natural Science Foundation of China(52274295)the Natural Science Foundation of Hebei Province(E2025501032,E2025501028)+3 种基金the Fundamental Research Funds for the Central Universities(N2523045,N2423051,N2423005,N2423019)the Science and Technology Project of Hebei Education Department(QN2024238)the Central Guided Local Science and Technology Development Fund Project of Hebei Province(254Z1102G)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)。
文摘The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.
基金supported by the National Natural Science Foundation of China(Grant No.W2412060,22325902 and 52171215)the State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2023002)。
文摘Sodium-ion batteries(SIBs)have attracted significant attention in large-scale energy storage system because of their abundant sodium resource and cost-effectiveness.Layered oxide materials are particularly promising as SIBs cathodes due to their high theoretical capacities and facile synthesis.However,their practical applications are hindered by the limitations in energy density and cycling stability.The comprehensive understanding of failure mechanisms within bulk structure and at the cathode/electrolyte interface of cathodes is still lacking.In this review,the issues related to bulk phase degradation and surface degradation,such as irreversible phase transitions,cation migration,transition metal dissolution,air/moisture instability,intergranular cracking,interfacial reactions,and reactive oxygen loss,are discussed.The latest advances and strategies to improve the stability of layered oxide cathodes and full cells are provided,as well as our perspectives on the future development of SIBs.
基金financially supported by the National Natural Science Foundation of China(NSFC)(52274295)the Natural Science Foundation of Hebei Province(E2021501029)+3 种基金the Fundamental Research Funds for the Central Universities(N2423051,N2423053,N2302016,N2423019,N2323013,N2423005)the Science and Technology Project of Hebei Education Department(QN2024238)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)the Science and Technology Project of Qinhuangdao City in 2023.
文摘Mn-based layered oxides(KMO)have emerged as one of the promising low-cost cathodes for potassiumion batteries(PIBs).However,due to the multiple-phase transitions and the distortion in the MnO6structure induced by the Jahn-Teller(JT)effect associated with Mn-ion,the cathode exhibits poor structural stability.Herein,we propose a strategy to enhance structural stability by introducing robust metal-oxygen(M-O)bonds,which can realize the pinning effect to constrain the distortion in the transition metal(TM)layer.Concurrently,all the elements employed have exceptionally high crustal abundance.As a proof of concept,the designed K_(0.5)Mn_(0.9)Mg_(0.025)Ti_(0.025)Al_(0.05)O_(2)cathode exhibited a discharge capacity of approximately 100 mA h g^(-1)at 20 mA g^(-1)with 79%capacity retention over 50 cycles,and 73%capacity retention over 200 cycles at 200 mA g^(-1),showcased much better battery performance than the designed cathode with less robust M-O bonds.The properties of the formed M-O bonds were investigated using theoretical calculations.The enhanced dynamics,mitigated JT effect,and improved structural stability were elucidated through the in-situ X-ray diffractometer(XRD),in-situ electrochemical impedance spectroscopy(EIS)(and distribution of relaxation times(DRT)method),and ex-situ X-ray absorption fine structure(XAFS)tests.This study holds substantial reference value for the future design of costeffective Mn-based layered cathodes for PIBs.
基金supported by the National Natural Science Foundation of China(no.52374301)the Open Project of Guangxi Key Laboratory of Electrochemical Energy Materials(no.GXUEEM2024001)+2 种基金the Hebei Provincial Natural Science Foundation(no.E2024501010)the Shijiazhuang Basic Research Project(no.241790667A)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)。
文摘Sodium-ion batteries(SIBs)have the advantages of environmental friendliness,cost-effectiveness,and high energy density,which are considered one of the most promising candidates for lithium-ion batteries(LIBs).The cathode materials influence the cost and energy output of SIBs.Therefore,the development of advanced cathode materials is crucial for the practical application of SIBs.Among various cathode materials,layered transition metal oxides(LTMOs)have received widespread attention owing to their straightforward preparation,abundant availability,and cost-competitiveness.Notably,layered Fe-based oxide cathodes are deemed to be one of the most promising candidates for the lowest price and easy-to-improve performance.Nevertheless,the challenges such as severe phase transitions,sluggish diffusion kinetics and interfacial degradation pose significant hurdles in achieving high-performance cathodes for SIBs.This review first briefly outlines the classification of layered structures and the working principle of layered oxides.Then,recent advances in modification strategies employed to address current issues with layered iron-based oxide cathodes are systematically reviewed,including ion doping,biphasic engineering and surface modification.Furthermore,the review not only outlines the prospects and development directions for layered Fe-based oxide cathodes but also provides novel insights and directions for future research endeavors for SIBs.
基金supported by the National Natural Science Foundation of China(52272295,52071137,51977071,51802040,and 21802020)the Science and Technology Innovation Program of Hunan Province(2021RC3066 and 2021RC3067)+2 种基金the Natural Science Foundation of Hunan Province(2020JJ3004 and 2020JJ4192)Graduate Research Innovation Project of Hunan Province(CX20240456 and CX20240405)N.Zhang and X.Xie also acknowledge the financial support of the Fundamental Research Funds for the Central。
文摘P2-type layered oxide Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)(NM)is a promising cathode material for sodium-ion batteries(SIBs).However,the severe irreversible phase transition,sluggish Na+diffusion kinetics,and interfacial side reactions at high-voltage result in grievous capacity degradation and inferior electrochemical performance.Herein,a dual-function strategy of entropy tuning and artificial cathode electrolyte interface(CEI)layer construction is reported to generate a novel P2-type medium-entropy Na_(0.75)Li_(0.1)Mg_(0.05)Ni_(0.18)Mn_(0.66)Ta_(0.01)O_(2)with NaTaO_(3)surface modification(LMNMT)to address the aforementioned issues.In situ X-ray diffraction reveals that LMNMT exhibits a near zero-strain phase transition with a volume change of only 1.4%,which is significantly lower than that of NM(20.9%),indicating that entropy tuning effectively suppresses irreversible phase transitions and enhances ion diffusion.Kinetic analysis and post-cycling interfacial characterization further confirm that the artificial CEI layer promotes the formation of a stable,thin NaF-rich CEI and reduces interfacial side reactions,thereby further enhancing ion transport kinetics and surface/interface stability.Consequently,the LMNMT electrode exhibits outstanding rate capability(46 mA h g^(−1)at 20 C)and cycling stability(89.5%capacity retention after 200 cycles at 2 C)within the voltage range of 2–4.35 V.The LMNMT also exhibits superior all-climate performance and air stability.This study provides a novel path for the design of high-voltage cathode materials for SIBs.
基金financially supported by the National Natural Science Foundation of China(52072036,52272187)the China Petroleum&Chemical Corporation(SINOPEC)project(223128).
文摘All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.
基金supported by the National Natural Science Foundation of China(22379121)the Shenzhen Foundation Research Fund(JCYJ20210324104412034)+1 种基金the Fundamental Research Funds for the Central Universities(G2024KY05103)the“Scientists+Engineers”Team in Qinchuangyuan of Shaanxi Province(2024QCY-KXJ-023)。
文摘Ni-rich layered oxide cathode materials such as LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)face poor interfacial stability and serious side reactions with sulfide solid-state electrolytes.This problem is thought to be exacerbated by the gradually accumulated basicity of the surface with the Ni content increasing.Herein,the acidic Li_(3)PO_(4)coating layer on NCM811 particles is introduced by ball-milling approach to neutralize the basicity and aggrandize the interfacial stability.The tailored surface structure and components of NCM811 not only suppress the direct contact of cathode particles with sulfide solid-state electrolyte,but also facilitate electrochemical dynamics by driving the Li+migration across the interface and promoting the electron exchange.Thus,cells with Li_(3)PO_(4)coating layer yield 101.3 mAh g^(-1)specific capacity at 2.0 C and highly reversed discharging capacity after suffering from harsh work conditions.Additionally,the stable coating layer broadens the electrochemical windows of cells,delivering long cycle stability(>100 cycles 0.5 C).This contribution highlights the importance of basicity regulation of Ni-rich layered oxide cathode and offers a low-cost and effective approach to design the interfacial structures for the development of all solid-state batteries.
基金funding support from the Beijing Natural Science Foundation(2252055)National Natural Science Foundation of China(52072033)BIT Research and Innovation Promoting Project(2024YCXY040,GIIP2023-34)。
文摘Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at high voltage.In this work,the strategy of the electron donor was utilized to address this issue.Remarkably,the earth-abundant P2-layered cathode Na_(2/3)Al_(1/6)Fe_(1/6)Mn_(2/3)O_(2)with the presence of K_(2)S renders superior rate capability(187.4 and 79.5 mA h g^(-1)at 20 and 1000 mA g^(-1))and cycling stability(a capacity retention of 85.6% over 300 cycles at 1000 mA g^(-1))within the voltage region of 2-4.4 V Na^(+)/Na.Furthermore,excellent electrochemical performance is also demonstrated in the full cell.Detailed structural analysis of as-proposed composite cathode illustrates that even at 4.4 V irreversible phase transition can be avoided as well as a cell volume variation of only 0.88%,which are attributed to the enhanced performance compared with the control group.Meanwhile,further investigation of charge compensation reveals the crucial role of sulfur ions in actively control of reversible redox reaction of oxygen species in the lattice structure.This work inspires a new strategy to enhance the structural stability of layered sodium ion cathode materials at high voltages.
基金financially supported by the National Natural Science Foundation of China(No.52071073,52177208,and 52171202)the Hebei Province“333 talent project”(No.C20221012)+2 种基金the Science and Technology Project of Hebei Education Department(BJK2023005)the Fundamental Research Funds for the Central Universities(2024GFZD002)the Natural Science Foundation of Hebei Province(E2024501015)。
文摘O3-type layered oxide cathodes for sodium-ion batteries are promising owing to high theoretical capacity and broad temperature adaptability,yet hindered by structural degradation and sluggish Na^(+)diffusion kinetics.Herein,we present a sodium-deficient high-entropy layered oxide cathode(Na_(0.85)Ni_(0.3)Mn_(0.3)Fe_(0.1)Co_(0.15)Ti_(0.1)Cu_(0.05)B_(0.02)O_(2),denoted as Na0.85-HEO),combining sodium content optimization and high-entropy composition design.Incorporating six transition metals and light element boron creates a unique high-entropy configuration,effectively mitigating local lattice distortion and internal strain through chemical disorder effects,thereby enabling highly reversible phase transitions(O3-P3-O3)and smaller volume change(0.6A^(3))during the initial cycle.The sodium-deficient high-entropy design effectively increases the sodium interlayer spacing to 0.322 nm,facilitating the Na^(+)diffusion kinetics.Moreover,this high-entropy strategy enables the cathode to have a completely solid solution charge curve and significantly reduces the proportion of(O_(2))^(n-),thereby suppressing gas release during the cycling process.The resultant cathode demonstrates exceptional cyclability(80% capacity retention after 400 cycles at 100 mA g^(-1)in a full cell),and remarkable low-temperature performance(108.6 mAh g^(-1)at -40℃).This work guides the design of high-entropy electrode materials with tailored ionic transport channels for extreme-temperature energy storage applications.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB2502000National Natural Science Foundation of China,Grant/Award Number:52207244。
文摘In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.
基金National Natural Science Foundation of China(52202327)Science and Technology Commission of Shanghai Municipality(22ZR1471300)+2 种基金National Science Foundation of China(Grant 51972326)Youth Innovation Promotion Association CAS,Foundation Strengthening ProjectProgram of Shanghai Academic Research Leader(Grant 22XD1424300).
文摘Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.
基金supported by the National Key R&D Program of China(Grant No.2017YFE0127600)the National Natural Science Foundation of China(Grant No.U1706229、21901248)+2 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDA22010600)the National Natural Science Foundation for Distinguished Young Scholars of China(No.51625204)the Taishan Scholars of Shandong Province(ts201511063)。
文摘In advantages of their high capacity and high operating voltage,the nickel(Ni)-rich layered transition metal oxide cathode materials(LiNi_(x)Co_(y)Mn_(z)O_(2)(NCMxyz,x+y+z=1,x≥0.5)and LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA))have been arousing great interests to improve the energy density of LIBs.However,these Nirich cathodes always suffer from rapid capacity degradation induced by unstable cathode-electrolyte interphase(CEI)layer and destruction of bulk crystal structure.Therefore,varied electrode/electrolyte interface engineering strategies(such as electrolyte formulation,material coating or doping)have been developed for Ni-rich cathodes protection.Among them,developing electrolyte functional additives has been proven to be a simple,effective,and economic method to improve the cycling stability of Nirich cathodes.This is achieved by removing unfavorable species(such as HF,H_(2)O)or constructing a stable and protective CEI layer against unfavorable reactive species(such as HF,H_(2)O).Herein,this review mainly introduces the varied classes of electrolyte functional additives and their working mechanism for interfacial engineering of Ni-rich cathodes.Especially,key favorable species for stabilizing CEI layer are summarized.More importantly,we put forward perspectives for screening and customizing ideal functional additives for high performance Ni-rich cathodes based LIBs.
基金financially supported partly by the National Key Research and Development Program of China(2018YFE0111600)Tianjin Sci.&Tech.Program(17YFZCGX00560,18ZXJMTG00040,19JCZDJC31800)。
文摘The interfacial instability between Ni-rich layered oxide cathodes and sulfide electrolytes is a serious problem,leading to poor electrochemical properties of all-solid-state lithium batteries(ASSLB).The chemical/electrochemical side reactions are considered to be the origin of the interfacial deterioration.However,the influence of chemical and electrochemical side reactions on the interfacial deterioration is rarely studied specifically.In this work,the deterioration mechanism of the interface between LiNi0.85-xCo0.15AlxO2 and Li10GeP2S12 is investigated in detail by combining in/ex-situ Raman spectra and Electrochemical Impedance Spectroscopy(EIS).It can be determined that chemical side reaction between LiNi0.8Co0.15Al0.05O2 and Li10GeP2S12 will occur immediately once contacted,and the interfacial deterioration becomes more serious after charge-discharge process under the dual effects of chemical and electrochemical side reactions.Moreover,our research reveals that the interfacial stability and the cycle performance of ASSLB can be greatly enhanced by increasing Al-substitution for Ni in LiNi0.85-xCo0.15AlxO2.In particular,the capacity retention of LiNi0.6Co0.15Al0.25O2 cathode after 200 cycles can reach 81.9%,much higher than that of LiNi0.8Co0.15Al0.05O2 cathode(12.5%@200 cycles).This work gives an insight to study the interfacial issues between Ni-rich layered oxide cathode and sulfide electrolyte for ASSLBs.
基金supported by the National Natural Science Foundation of China (52173273)Fundamental Research Funds for the Central Universities (2022CX11013)+2 种基金Shanxi Province Science Foundation for Youths (No.202203021212391)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (No.2022L253)Institute Foundation Project of China Academy of Railway Sciences Corporation Limited Metals and Chemistry Research Institute (No.2023SJ02)。
文摘The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.
基金Project supported by the National Natural Science Foundation of China (Grant No.11905076)S&T Program of Hebei (Grant No.SZX2020034)。
文摘A novel emissive probe consisting of an oxide cathode coating is developed to achieve a low operating temperature and long service life.The properties of the novel emissive probe are investigated in detail,in comparison with a traditional tungsten emissive probe,including the operating temperature,the electron emission capability and the plasma potential measurement.Studies of the operating temperature and electron emission capability show that the tungsten emissive probe usually works at a temperature of 1800 K-2200 K while the oxide cathode emissive probe can function at about 1200 K-1400 K.In addition,plasma potential measurements using the oxide cathode emissive probe with different techniques have been accomplished in microwave electron cyclotron resonance plasmas with different discharge powers.It is found that a reliable plasma potential can be obtained using the improved inflection point method and the hot probe with zero emission limit method,while the floating point method is invalid for the oxide cathode emissive probe.
基金supported by the National Natural Science Foundation of China(Grant No.12105197 and 52088101)Guangdong Basic and Applied Basic Research Foundation(Grant No.2022A1515010319)+1 种基金the open research fund of Songshan Lake Materials Laboratory(No.2022SLABFK04)Large Scientific Facility Open Subject of Songshan Lake,Dongguan,Guangdong
文摘Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.
基金financially supported by the National Key R&D Program of China(2016YFB0700600)the Soft Science Research Project of Guangdong Province(No.2017B030301013)the Shenzhen Science and Technology Research Grant(ZDSYS201707281026184)。
文摘Li and Mn rich(LMR)layered oxides,written as xLi_(2) MnO_(3)·(1-x)LiMO_(2)(M=Mn,Ni,Co,Fe,etc.),have been widely reported in recent years due to their high capacity and high energy density.The stable structure and superior performance of LMR oxides make them one of the most promising candidates for the next-generation cathode materials.However,the commercialization of these materials is hindered by several drawbacks,such as low initial Coulombic efficiency,the degradation of voltage and capacity during cycling,and poor rate performance.This review summarizes research progress in solving these concerns of LMR cathodes over the past decade by following three classes of strategies:morphology design,bulk design,and surface modification.We elaborate on the processing procedures,electrochemical performance,mechanisms,and limitations of each approach,and finally put forward the concerns left and the possible solutions for the commercialization of LMR cathodes.
基金supported by the National Natural Science Foundation of China(Grant No.21872058)the Key Project of Science and Technology in Guangdong Province(2017A010106006)
文摘Lithium-rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium-rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium-rich oxide phase transformation and established a clear correlation between the successive consumption of Li+on anode due to incessant interphase repairing and the over-delithiation of lithium-rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium-rich oxide cathode, leading to high capacity and cycling stability.
