Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selecte...Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selected.Their surface oxide layers formed during the solidification are characterized in detail,and the corresponding oxidation mechanisms are discussed.The results reveal that RE elements obviously influence the characteristics of surface oxide layers,which depends on their ability to purify the formed MgO in the melt via the reaction(2RE+3MgO=3Mg+RE_(2)O_(3)).On the one hand,as Nd and Gd do not easily displace MgO already formed in the melt,the loose oxide layers in NZ30K and EV33 alloys are mainly composed of MgO matrix with embedded RE-rich oxide particles.On the other hand,due to the strong ability of Y to purify MgO in the melt,the oxide layer of WE43A alloy becomes a denser and thinner Y_(2)O_(3) oxide layer.Note that the differences in surface oxide layers well explain the different secondary inclusions that occur in three typical Mg-RE alloys during the casting process.展开更多
Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower...Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.展开更多
The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding o...The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding of Al alloy retaining continuous oxide layers was successfully achieved in the air by a low-temperature and low-pressure diffusion bonding mothed using a Zn interlayer.During the bonding processes,conducted at 360℃ and 3 MPa,Zn diffused into Al through cracks of thin oxide layers to form the joint composed Al/(diffusion layer)/(oxide layer)/(Zn)/(oxide layer)/(diffusion layer)/Al.The diffusion layers were composed of Zn-Al eutectoid,and the oxide layer included nanocrystals and amorphous Al_(2)O_(3).The shear strength of joints containing continuous oxide layers was about 30 MPa.Interestingly,the migration behavior toward the joint center of the interfacial oxide layers was observed with consuming of the Zn interlayer.The cracking phenomenon,the“subcutaneous diffusion”and the migration behavior of oxide layers were verified and analyzed by the diffusion bonding of anodized 6063Al-6063Al.Subsequently,the dynamic migration mechanism of oxide layers with elements diffusion and bonding interface strengths were discussed in detail.The ability to join Al alloys in the air at low temperatures and low pressure suggests a highly practical and economic method for diffusion bonding.展开更多
Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultra...Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultrathin permalloy films was studied. The results show that the influence of grain size and textures on the MR ratio becomes weak when the thickness of the NiFe layer is below 15 nm. A higher MR ratio was observed for the thinner （〈 15 nm） NiFe film with NOLs. The MR ratio of a 10 nm NiFe film can be remarkably enhanced by NOLs. The enhanced MR ratio for these ultrathin films can be attributed to the enhanced specular reflection of conduction electrons.展开更多
Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-...Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.展开更多
Based on the quantum confinement-luminescence center model, to ensembles of spherical silicon nanocrystals (nc-Si) containing two kinds of luminescence centers (LCs) in the layers surrounding the nc-Si, the relations...Based on the quantum confinement-luminescence center model, to ensembles of spherical silicon nanocrystals (nc-Si) containing two kinds of luminescence centers (LCs) in the layers surrounding the nc-Si, the relationship between the photoluminescence (PL) and the thickness of the layer is studied with the excitation energy flux density as a parameter. When there is no layer surrounding the nc-Si, the electron-heavy hole pair can only recombine inside the nc-Si, then the PL blueshift with reducing particle sizes roughly accords with the rule predicted by the quantum confinement model of Canham. When there presences a layer, some of the carriers may tunnel into it and recombine outside the nc-Si at the LCs to emit visible light. The thicker the layer is, the higher the radiative recombination rate occurred outside the nc-Si will be. When the central scale of the nc-Si is much smaller than the critical scale, the radiative recombination rate outside the nc-Si dominates, and visible PL will be possible for some nc-Si samples with big average radius, greater than 4 nm, for example. When there is only one kind of LC in the layer, the PL peak position does not shift with reducing particle sizes. All these conclusions are in accord with the experimental results. When there are two or more kinds of LCs in the layer, the PL peak position energy and intensity swing with reducing particle sizes.展开更多
Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capac...Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.展开更多
The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the ...The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.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
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitio...Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitions and unfavorable interfacial side reactions accelerate capacity and voltage decay.Herein,we present a straightforward melting plus reactive wetting strategy using H_(3)BO_(3)for surface modification of O_(3)-type Na_(0.9)Cu_(0.12)Ni_(0.33)Mn_(0.4)Ti_(0.15)O_(2)(CNMT).The transformation of H_(3)BO_(3)from solid to liquid under mild heating facilitates the uniform dispersion and complete surface coverage of CNMT particles.By neutralizing the residual alkali and extracting Na^(+)from the CNMT lattice,H_(3)BO_(3)forms a multifunctional Na_(2)B_(2)O_(5)-dominated layer on the CNMT surface.This Na_(x)B_(y)O_(z)(NBO)layer plays a positive role in providing low-barrier Na^(+)transport channels,suppressing phase transitions,and minimizing the generation of O_(2)/CO_(2)gases and resistive byproducts.As a result,at a charge cutoff voltage of 4.5 V,the NBO-coated CNMT delivers a high discharge capacity of 149,1 mAh g^(-1)at 10 mA g^(-1)and exhibits excellent cycling stability at 100 mA g^(-1)over 200 cycles with a higher capacity retention than that of pristine CNMT(86,4%vs,62.1%).This study highlights the effectiveness of surface modification using lowmelting-point solid acids,with potential applications for other layered oxide cathode materials to achieve stable high-voltage cycling.This proposed strategy opens new avenues for the construction of highquality coatings for high-voltage layered oxide cathodes in SIBs.展开更多
Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by th...Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by the Jahn-Teller effect of Mn^(3+)and the large ionic radius of K+results in poor electrochemical performance.Herein,we propose an effective structural stabilization strategy for P2-type Mn-based layered oxide cathodes of KIBs through Li-incorporation into the transition metal layer.Using the firstprinciples calculations and experiments,we demonstrate that the P2-K_(0.48)[Li_(0.1)Mn_(0.9)]O_(2)(P2-KLMO)delivers improved electrochemical performance,specific capacity and average discharge voltage of~124.4 m A h g^(-1)and~2.7 V(vs.K^(+)/K)at 0.05C(1C=260 mA g^(-1)),outperforming P2-K_(0.5)MnO_(2).Operando X-ray diffraction analysis confirms the P2-OP4 phase transition and Mn^(3+)-induced Jahn-Teller distortion are significantly suppressed in P2-KLMO.These improvements are attributed to the lithium introduction into transition metal layers,leading to strengthened structural stability and enhanced K+diffusion kinetics.Moreover,synthetic accessibility through the conventional solid-state method provides an additional advantage for practical application of Li-incorporated Mn-based P2-type cathodes in KIBs.We believe our study offers a simple yet effective strategy for designing highperformance and practical cathode materials for KIBs.展开更多
Sodium-ion batteries(SIBs)employ P2-type layered transition metal oxides as promising cathode materials,primarily due to their abundant natural reserves and environmentally friendly characteristics.However,structural ...Sodium-ion batteries(SIBs)employ P2-type layered transition metal oxides as promising cathode materials,primarily due to their abundant natural reserves and environmentally friendly characteristics.However,structural instability and complex phase transitions during electrochemical cycling pose significant challenges to their practical applications.Employing cation substitution serves as a straightforward yet effective strategy for stabilizing the structure and improving the kinetics of the active material.In this study,we introduce a Ni-rich honeycomb-layered Na_(2+x)Ni_(2)TeO_(6)(NNTO)cathode material with variable sodium content(x=0,0.03,0.05,0.10).Physicochemical characterizations reveal that excess sodium content at the atomic scale modifies the surface and suppresses phase transitions,while preserving the crystal structure.This results in enhanced cyclic performance and improved electrochemical kinetics at room temperature.Furthermore,we investigate the performance of the NNTO cathode material containing 10%excess sodium at a relatively high temperature of 60℃,where it exhibits 71.6%capacity retention compared to 60%for the pristine.Overall,our results confirm that a preconstructed surface layer(induced by excess sodium)effectively safeguards the Ni-based cathode material from surface degradation and phase transitions during the electrochemical processes,thus exhibiting superior capacity retention relative to the pristine NNTO cathode.This study of the correlation between structure and performance can potentially be applied to the commercialization of 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
The detrimental phase transformations of sodium layered transition metal oxides(Na_(x)TMO_(2))during desodiation/sodiation seriously suppress their practical applications for sodium ion batteries(SIBs).Undoubtedly,com...The detrimental phase transformations of sodium layered transition metal oxides(Na_(x)TMO_(2))during desodiation/sodiation seriously suppress their practical applications for sodium ion batteries(SIBs).Undoubtedly,comprehensively investigating of the dynamic crystal structure evolutions of Na_(x)TMO_(2)associating with Na ions extraction/intercalation and then deeply understanding of the relationships between electrochemical performances and phase structures drawing support from advanced characterization techniques are indispensable.In-situ high-energy X-ray diffraction(HEXRD),a powerful technology to distinguish the crystal structure of electrode materials,has been widely used to identify the phase evolutions of Na_(x)TMO_(2)and then profoundly revealed the electrochemical reaction processes.In this review,we begin with the descriptions of synchrotron characterization techniques and then present the advantages of synchrotron X-ray diffraction(XRD)over conventional XRD in detail.The optimizations of structural stability and electrochemical properties for P2-,O3-,and P2/O3-type Na_(x)TMO_(2)cathodes through single/dual-site substitution,high-entropy design,phase composition regulation,and surface engineering are summarized.The dynamic crystal structure evolutions of Na_(x)TMO_(2)polytypes during Na ion extraction/intercalation as well as corresponding structural enhancement mechanisms characterizing by means of HEXRD are concluded.The interior relationships between structure/component of Na_(x)TMO_(2)polytypes and their electrochemical properties are discussed.Finally,we look forward the research directions and issues in the route to improve the electrochemical properties of Na_(x)TMO_(2)cathodes for SIBs in the future and the combined utilizations of multiple characterization techniques.This review will provide significant guidelines for rational designs of high-performance Na_(x)TMO_(2)cathodes.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
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
The O3-type layered cathode with high Ni content has attracted much attention because of its high capacity and simple synthesis process.However,surface side reaction and O3-P3 phase transitions would occur during Na+i...The O3-type layered cathode with high Ni content has attracted much attention because of its high capacity and simple synthesis process.However,surface side reaction and O3-P3 phase transitions would occur during Na+insertion/extraction,resulting in unsatisfying electrochemical performance.Herein,O3-Na[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NNCM622)cathode is modified by a NaTiOx coating layer in a wet chemistry method,which reduces the parasitic reaction and facilitates Na+migration.Simultaneously,the partially doped Ti improves structural stability by restraining the irreversible multiple-phase transition.As a result,the modified NNCM622 cathode obtains a high specific capacity of 143.4 mAh g^(−1)and an improved capacity retention of 69%after 300 cycles.Our work offers new prospects for stabilizing the NNCM622 cathode with a feasible coating strategy.展开更多
In the field of lithium-ion battery cathode materials, lithium-rich layered oxide materials have garnered significant attention due to their exceptional discharge specific capacity and high operating voltage. However,...In the field of lithium-ion battery cathode materials, lithium-rich layered oxide materials have garnered significant attention due to their exceptional discharge specific capacity and high operating voltage. However, their limitations in terms of cycling stability and rate capability remain major impediments to their wider application. In this study, an innovative approach was employed by simultaneously utilizing the acidic and oxidative properties of phosphomolybdic acid to generate a spinel structure and in-situ coating of a conductive polymer(polypyrrole) on the surface of lithium-rich layered oxide materials. This strategy aimed to mitigate structural degradation during charge-discharge cycles, enhance the ionic/electronic conductivity, and suppress side reactions. Experimental results demonstrated that after 200 cycles at a current density of 1 C, the modified sample exhibited a discharge specific capacity of 193.4 m Ah/g, with an improved capacity retention rate of 83.3% and a minimal voltage decay of only 0.27 V. These findings provide compelling support for the development and application of next-generation high-performance lithium-ion batteries.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U2037601 and 51821001)Major Scientific and Technological Innovation Projects in Luoyang(No.2201029A)the Research Program of Joint Research Center of Advanced Spaceflight Technologies(Nos.USCAST2020–14 and USCAST2020–31).
文摘Surface oxide layers play a significant role in forming secondary oxidation inclusions during the casting process.In this study,three typical Mg-RE alloys(Mg-3Nd(NZ30K),Mg-3Nd-3Gd(EV33)and Mg-3Nd-4Y(WE43A))are selected.Their surface oxide layers formed during the solidification are characterized in detail,and the corresponding oxidation mechanisms are discussed.The results reveal that RE elements obviously influence the characteristics of surface oxide layers,which depends on their ability to purify the formed MgO in the melt via the reaction(2RE+3MgO=3Mg+RE_(2)O_(3)).On the one hand,as Nd and Gd do not easily displace MgO already formed in the melt,the loose oxide layers in NZ30K and EV33 alloys are mainly composed of MgO matrix with embedded RE-rich oxide particles.On the other hand,due to the strong ability of Y to purify MgO in the melt,the oxide layer of WE43A alloy becomes a denser and thinner Y_(2)O_(3) oxide layer.Note that the differences in surface oxide layers well explain the different secondary inclusions that occur in three typical Mg-RE alloys during the casting process.
基金financially supported by the Scientific and Technological Plan Project of Guizhou Province (Grant No. [2021]060)the Industry and Education Combination Innovation Platform of Intelligent Manufacturing and the Graduate Joint Training Base at Guizhou University (Grant No. 2020-520000-83-01-324061)the Guizhou Engineering Research Center for smart services (Grant No. 2203-520102-04-04-298868)。
文摘Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.
基金supported by the National Natural Science Foundation of China under Grant No.51975152.
文摘The oxide layer on the surface has always been a key obstacle to achieving the diffusion bonding of Al alloys.It is a challenge for performing diffusion bonding without removing oxide layers.Herein,diffusion bonding of Al alloy retaining continuous oxide layers was successfully achieved in the air by a low-temperature and low-pressure diffusion bonding mothed using a Zn interlayer.During the bonding processes,conducted at 360℃ and 3 MPa,Zn diffused into Al through cracks of thin oxide layers to form the joint composed Al/(diffusion layer)/(oxide layer)/(Zn)/(oxide layer)/(diffusion layer)/Al.The diffusion layers were composed of Zn-Al eutectoid,and the oxide layer included nanocrystals and amorphous Al_(2)O_(3).The shear strength of joints containing continuous oxide layers was about 30 MPa.Interestingly,the migration behavior toward the joint center of the interfacial oxide layers was observed with consuming of the Zn interlayer.The cracking phenomenon,the“subcutaneous diffusion”and the migration behavior of oxide layers were verified and analyzed by the diffusion bonding of anodized 6063Al-6063Al.Subsequently,the dynamic migration mechanism of oxide layers with elements diffusion and bonding interface strengths were discussed in detail.The ability to join Al alloys in the air at low temperatures and low pressure suggests a highly practical and economic method for diffusion bonding.
基金supported by the National Science Foundation of China (Nos.50671008,50871014,and 50831002)
文摘Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultrathin permalloy films was studied. The results show that the influence of grain size and textures on the MR ratio becomes weak when the thickness of the NiFe layer is below 15 nm. A higher MR ratio was observed for the thinner （〈 15 nm） NiFe film with NOLs. The MR ratio of a 10 nm NiFe film can be remarkably enhanced by NOLs. The enhanced MR ratio for these ultrathin films can be attributed to the enhanced specular reflection of conduction electrons.
文摘Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.
文摘Based on the quantum confinement-luminescence center model, to ensembles of spherical silicon nanocrystals (nc-Si) containing two kinds of luminescence centers (LCs) in the layers surrounding the nc-Si, the relationship between the photoluminescence (PL) and the thickness of the layer is studied with the excitation energy flux density as a parameter. When there is no layer surrounding the nc-Si, the electron-heavy hole pair can only recombine inside the nc-Si, then the PL blueshift with reducing particle sizes roughly accords with the rule predicted by the quantum confinement model of Canham. When there presences a layer, some of the carriers may tunnel into it and recombine outside the nc-Si at the LCs to emit visible light. The thicker the layer is, the higher the radiative recombination rate occurred outside the nc-Si will be. When the central scale of the nc-Si is much smaller than the critical scale, the radiative recombination rate outside the nc-Si dominates, and visible PL will be possible for some nc-Si samples with big average radius, greater than 4 nm, for example. When there is only one kind of LC in the layer, the PL peak position does not shift with reducing particle sizes. All these conclusions are in accord with the experimental results. When there are two or more kinds of LCs in the layer, the PL peak position energy and intensity swing with reducing particle sizes.
基金financially supported by the National Natural Science Foundation of China(No.12304077)the Natural Science Foundation of Science and Technology Department of Sichuan Province(No.23NSFSC6224)+3 种基金Sichuan Science and Technology Program(No.2024NSFSC0989)the Key Laboratory of Computational Physics of Sichuan Province(No.YBUJSWL-YB-2022-03)the Material Corrosion and Protection Key Laboratory of Sichuan Province(No.2023CL14 and No.2023CL01)the National Innovation Practice Project(No.202411079005S).
文摘Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.
基金supported by the National Key R&D Program of China(No.2022YFB2404400)the National Natural Science Foundation of China(Nos.U23A20577,52372168,92263206 and 21975006)+1 种基金the“The Youth Beijing Scholars program”(No.PXM2021_014204_000023)the Beijing Natural Science Foundation(Nos.2222001 and KM202110005009).
文摘The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.
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.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
基金supported by the National Natural Science Foundation of China(22169002 and 22469003)the Chongzuo Key Research and Development Program of China(20241205 and 20231204)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)。
文摘Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitions and unfavorable interfacial side reactions accelerate capacity and voltage decay.Herein,we present a straightforward melting plus reactive wetting strategy using H_(3)BO_(3)for surface modification of O_(3)-type Na_(0.9)Cu_(0.12)Ni_(0.33)Mn_(0.4)Ti_(0.15)O_(2)(CNMT).The transformation of H_(3)BO_(3)from solid to liquid under mild heating facilitates the uniform dispersion and complete surface coverage of CNMT particles.By neutralizing the residual alkali and extracting Na^(+)from the CNMT lattice,H_(3)BO_(3)forms a multifunctional Na_(2)B_(2)O_(5)-dominated layer on the CNMT surface.This Na_(x)B_(y)O_(z)(NBO)layer plays a positive role in providing low-barrier Na^(+)transport channels,suppressing phase transitions,and minimizing the generation of O_(2)/CO_(2)gases and resistive byproducts.As a result,at a charge cutoff voltage of 4.5 V,the NBO-coated CNMT delivers a high discharge capacity of 149,1 mAh g^(-1)at 10 mA g^(-1)and exhibits excellent cycling stability at 100 mA g^(-1)over 200 cycles with a higher capacity retention than that of pristine CNMT(86,4%vs,62.1%).This study highlights the effectiveness of surface modification using lowmelting-point solid acids,with potential applications for other layered oxide cathode materials to achieve stable high-voltage cycling.This proposed strategy opens new avenues for the construction of highquality coatings for high-voltage layered oxide cathodes in SIBs.
基金supported by the National Research Foundation of Korea funded by the Ministry of Science and ICT of Korea(RS-2024-00408156)。
文摘Mn-based layered oxides are widely recognized as cathode materials for potassium-ion batteries(KIBs)due to their high specific capacity derived from their low molar mass.However,the structural instability caused by the Jahn-Teller effect of Mn^(3+)and the large ionic radius of K+results in poor electrochemical performance.Herein,we propose an effective structural stabilization strategy for P2-type Mn-based layered oxide cathodes of KIBs through Li-incorporation into the transition metal layer.Using the firstprinciples calculations and experiments,we demonstrate that the P2-K_(0.48)[Li_(0.1)Mn_(0.9)]O_(2)(P2-KLMO)delivers improved electrochemical performance,specific capacity and average discharge voltage of~124.4 m A h g^(-1)and~2.7 V(vs.K^(+)/K)at 0.05C(1C=260 mA g^(-1)),outperforming P2-K_(0.5)MnO_(2).Operando X-ray diffraction analysis confirms the P2-OP4 phase transition and Mn^(3+)-induced Jahn-Teller distortion are significantly suppressed in P2-KLMO.These improvements are attributed to the lithium introduction into transition metal layers,leading to strengthened structural stability and enhanced K+diffusion kinetics.Moreover,synthetic accessibility through the conventional solid-state method provides an additional advantage for practical application of Li-incorporated Mn-based P2-type cathodes in KIBs.We believe our study offers a simple yet effective strategy for designing highperformance and practical cathode materials for KIBs.
基金Korea Institute of Science and Technology,Grant/Award Number:2E33270National Research Foundation of Korea,Grant/Award Number:2020M3H4A3081889。
文摘Sodium-ion batteries(SIBs)employ P2-type layered transition metal oxides as promising cathode materials,primarily due to their abundant natural reserves and environmentally friendly characteristics.However,structural instability and complex phase transitions during electrochemical cycling pose significant challenges to their practical applications.Employing cation substitution serves as a straightforward yet effective strategy for stabilizing the structure and improving the kinetics of the active material.In this study,we introduce a Ni-rich honeycomb-layered Na_(2+x)Ni_(2)TeO_(6)(NNTO)cathode material with variable sodium content(x=0,0.03,0.05,0.10).Physicochemical characterizations reveal that excess sodium content at the atomic scale modifies the surface and suppresses phase transitions,while preserving the crystal structure.This results in enhanced cyclic performance and improved electrochemical kinetics at room temperature.Furthermore,we investigate the performance of the NNTO cathode material containing 10%excess sodium at a relatively high temperature of 60℃,where it exhibits 71.6%capacity retention compared to 60%for the pristine.Overall,our results confirm that a preconstructed surface layer(induced by excess sodium)effectively safeguards the Ni-based cathode material from surface degradation and phase transitions during the electrochemical processes,thus exhibiting superior capacity retention relative to the pristine NNTO cathode.This study of the correlation between structure and performance can potentially be applied to the commercialization of 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supported by the State Grid Corporation Science and Technology Project(No.5419-202158503A-0-5-ZN)。
文摘The detrimental phase transformations of sodium layered transition metal oxides(Na_(x)TMO_(2))during desodiation/sodiation seriously suppress their practical applications for sodium ion batteries(SIBs).Undoubtedly,comprehensively investigating of the dynamic crystal structure evolutions of Na_(x)TMO_(2)associating with Na ions extraction/intercalation and then deeply understanding of the relationships between electrochemical performances and phase structures drawing support from advanced characterization techniques are indispensable.In-situ high-energy X-ray diffraction(HEXRD),a powerful technology to distinguish the crystal structure of electrode materials,has been widely used to identify the phase evolutions of Na_(x)TMO_(2)and then profoundly revealed the electrochemical reaction processes.In this review,we begin with the descriptions of synchrotron characterization techniques and then present the advantages of synchrotron X-ray diffraction(XRD)over conventional XRD in detail.The optimizations of structural stability and electrochemical properties for P2-,O3-,and P2/O3-type Na_(x)TMO_(2)cathodes through single/dual-site substitution,high-entropy design,phase composition regulation,and surface engineering are summarized.The dynamic crystal structure evolutions of Na_(x)TMO_(2)polytypes during Na ion extraction/intercalation as well as corresponding structural enhancement mechanisms characterizing by means of HEXRD are concluded.The interior relationships between structure/component of Na_(x)TMO_(2)polytypes and their electrochemical properties are discussed.Finally,we look forward the research directions and issues in the route to improve the electrochemical properties of Na_(x)TMO_(2)cathodes for SIBs in the future and the combined utilizations of multiple characterization techniques.This review will provide significant guidelines for rational designs of high-performance Na_(x)TMO_(2)cathodes.
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:2023YFB2406100Yibin‘Jie Bang Gua Shuai’,Grant/Award Number:2022JB003National Natural Science Foundation of China,Grant/Award Number:52172234。
文摘The O3-type layered cathode with high Ni content has attracted much attention because of its high capacity and simple synthesis process.However,surface side reaction and O3-P3 phase transitions would occur during Na+insertion/extraction,resulting in unsatisfying electrochemical performance.Herein,O3-Na[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NNCM622)cathode is modified by a NaTiOx coating layer in a wet chemistry method,which reduces the parasitic reaction and facilitates Na+migration.Simultaneously,the partially doped Ti improves structural stability by restraining the irreversible multiple-phase transition.As a result,the modified NNCM622 cathode obtains a high specific capacity of 143.4 mAh g^(−1)and an improved capacity retention of 69%after 300 cycles.Our work offers new prospects for stabilizing the NNCM622 cathode with a feasible coating strategy.
基金supported partially by projects of National Natural Science Foundation of China (Nos. 52272200, 51972110, 52102245, 52102203 and 52072121)State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources (Nos. LAPS21004, LAPS202114)+5 种基金Beijing Natural Science Foundation (Nos. 2222076, 2222077)Hebei Natural Science Foundation (No. E2022502022)Huaneng Group Headquarters Science and Technology Project (No. HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education, China Postdoctoral Science Foundation (No. 2022M721129)the Fundamental Research Funds for the Central Universities (Nos. 2022MS030, 2021MS028, 2020MS023, 2020MS028)the NCEPU "Double First-Class" Program。
文摘In the field of lithium-ion battery cathode materials, lithium-rich layered oxide materials have garnered significant attention due to their exceptional discharge specific capacity and high operating voltage. However, their limitations in terms of cycling stability and rate capability remain major impediments to their wider application. In this study, an innovative approach was employed by simultaneously utilizing the acidic and oxidative properties of phosphomolybdic acid to generate a spinel structure and in-situ coating of a conductive polymer(polypyrrole) on the surface of lithium-rich layered oxide materials. This strategy aimed to mitigate structural degradation during charge-discharge cycles, enhance the ionic/electronic conductivity, and suppress side reactions. Experimental results demonstrated that after 200 cycles at a current density of 1 C, the modified sample exhibited a discharge specific capacity of 193.4 m Ah/g, with an improved capacity retention rate of 83.3% and a minimal voltage decay of only 0.27 V. These findings provide compelling support for the development and application of next-generation high-performance lithium-ion batteries.
