High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

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.

Difficulties, strategies, and recent research and development of layered sodium transition metal oxide cathode materials for high-energy sodium-ion batteries

Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.

Responses of the Southern Ocean mixed layer depth to the eastern and central Pacific El Niño events during austral winter

Based on the Ocean Reanalysis System version 5(ORAS5)and the fifth-generation reanalysis datasets derived from European Centre for Medium-Range Weather Forecasts(ERA5),we investigate the different impacts of the central Pacific(CP)El Niño and the eastern Pacific(EP)El Niño on the Southern Ocean(SO)mixed layer depth(MLD)during austral winter.The MLD response to the EP El Niño shows a dipole pattern in the South Pacific,namely the MLD dipole,which is the leading El Niño-induced MLD variability in the SO.The tropical Pacific warm sea surface temperature anomaly(SSTA)signal associated with the EP El Niño excites a Rossby wave train propagating southeastward and then enhances the Amundsen Sea low(ASL).This results in an anomalous cyclone over the Amundsen Sea.As a result,the anomalous southerly wind to the west of this anomalous cyclone advects colder and drier air into the southeast of New Zealand,leading to surface cooling through less total surface heat flux,especially surface sensible heat(SH)flux and latent heat(LH)flux,and thus contributing to the mix layer(ML)deepening.The east of the anomalous cyclone brings warmer and wetter air to the southwest of Chile,but the total heat flux anomaly shows no significant change.The warm air promotes the sea ice melting and maintains fresh water,which strengthens stratification.This results in a shallower MLD.During the CP El Niño,the response of MLD shows a separate negative MLD anomaly center in the central South Pacific.The Rossby wave train triggered by the warm SSTA in the central Pacific Ocean spreads to the Amundsen Sea,which weakens the ASL.Therefore,the anomalous anticyclone dominates the Amundsen Sea.Consequently,the anomalous northerly wind to the west of anomalous anticyclone advects warmer and wetter air into the central and southern Pacific,causing surface warming through increased SH,LH,and longwave radiation flux,and thus contributing to the ML shoaling.However,to the east of the anomalous anticyclone,there is no statistically significant impact on the MLD.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries

O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.

Inhibiting Voltage Decay in Li-Rich Layered Oxide Cathode:From O3-Type to O2-Type Structural Design

Li-rich layered oxide(LRLO)cathodes have been regarded as promising candidates for next-generation Li-ion batteries due to their exceptionally high energy density,which combines cationic and anionic redox activities.However,continuous voltage decay during cycling remains the primary obstacle for practical applications,which has yet to be fundamentally addressed.It is widely acknowledged that voltage decay originates from the irreversible migration of transition metal ions,which usually further exacerbates structural evolution and aggravates the irreversible oxygen redox reactions.Recently,constructing O2-type structure has been considered one of the most promising approaches for inhibiting voltage decay.In this review,the relationship between voltage decay and structural evolution is systematically elucidated.Strategies to suppress voltage decay are systematically summarized.Additionally,the design of O2-type structure and the corresponding mechanism of suppressing voltage decay are comprehensively discussed.Unfortunately,the reported O2-type LRLO cathodes still exhibit partially disordered structure with extended cycles.Herein,the factors that may cause the irreversible transition metal migrations in O2-type LRLO materials are also explored,while the perspectives and challenges for designing high-performance O2-type LRLO cathodes without voltage decay are proposed.

Role of Retinal Nerve Fiber Layer Thickness and Optic Disk Measurement by OCT onEarly Diagnosis of Glaucoma

Purpose:.Glaucoma is an eye disease that can lead to irreversible optic nerve damage and cause blindness. Optical coherence tomography.(OCT) allows an early diagnosis of glaucoma by the measurements of the retinal nerve fiber and optic disc parameters.A retrospective study was designed to analyze the effects of the measurement of the retinal nerve fiber layer(RNFL) thickness and the optic disc tomography by spectraldomain OCT on the early diagnosis of suspected glaucoma and primary open angle glaucoma(POAG).Methods:.This was a clinical case-control study. The RNFL thickness around the optic disc and optic disk tomographic parameters of the control(n=51, 98 eyes), suspected glaucoma(n=81,.146 eyes), and POAG groups(n=55, 106 eyes) were measured by OCT. The parameters included superior, inferior, nasal and temporal mean RNFL thickness,.disc area(DA), cup area(CA), rim area(RA), disc volume(DV),cup volume(CV), rim volume(RV), cup / disc area ratio(CA / DA), rim / disc area ratio(RA / DA), cup / disc volume ratio(CV / DV) and rim / disc volume ratio(RV / DV).Results: Superior, nasal, and mean RNFL parameters, DA,CA,RA, DV, CV, CA / DA, RA / DA, CV / DV and RV / DV significantly differed among three groups by single-factorial ANOVA. Inferior and temporal RNFL thickness significantly differed between the control and POAG groups. No significant difference was observed in RV among three groups. In the POAG group,.the maximum area under the ROC curve(AROC) of mean RNFL thickness was 0.845. The maximum AROC of optic disk parameters was RA / DA(0.998), followed by CA / DA(0.997). The AROC of CA, RA, CV, and DV were all > 0.900.Conclusion:.OCT may serve as a useful diagnostic modality in distinguishing suspected glaucoma from POAG.

Construction interlayer structure of hydrated vanadium oxides with tunable P-band center of oxygen towards enhanced aqueous Zn-ion batteries

Layered materials with adjustable framework,as the most potential cathode materials for aqueous rechargeable zinc ion batterie,have high capacity,permit of rapid ion diffusion,and charge transfer channels.Previous studies have widely investigated their preparation and storage mechanism,but the intrinsic relationship between the structural design of layered cathode materials and electrochemical performance has not been well established.In this work,based on the first principles calculations and experiments,a crucial strategy of pre-intercalated metalions in vanadium oxide interlayer with administrable p-band center(ε_(p))of O is explored to enhance Zn^(2+)storage.This regulation of the degree of covalent bond and the average charge of O atoms varies the binding energy between Zn^(2+)and O,thus affecting the intercalation/de-intercalation of Zn2þ.The present study demonstrates thatεp of O can be used as an important indicator to boost Zn2þstorage,which provides a new concept toward the controlled design and application of layered materials.

Effects of Orbital Motion on the Boundary Layer Flow on a Spinning Disk

The objective of this study is to experimentally examine the effects of orbital motion on the boundary layer flow on a spinning disk. The boundary layer flow on the disk is visualized by the oil flow method, and velocity in the boundary layer is measured by the hot-wire method. For the oil flow pattern in the case of spinning motion only, streaks are clearly observed on the disk as transient vortices, but by adding orbital motion to the spinning motion, we find that streaks are not observed in a certain range of orbital conditions. With increasing orbital motion speed, the laminar re- gion becomes narrower and transition is promoted from the inward region of the disk, regardless of the direction of ro- tation. Also, with the addition of orbital motion, the velocity profile in the boundary layer becomes more asymmetric with respect to the spin axis of the disk. Furthermore, stationary vortices do not appear on the disk when the orbital speed is beyond a certain critical value. Therefore, the lack of streaks in the oil film pattern when orbital motion is added is due to the spatiotemporal unsteadiness of the flow field on the disk.

Effects of Orbital Motion on the Velocity Field of Boundary Layer Flow over a Rotating Disk

The purpose of this study is to investigate experimentally the effects of orbital motion on the velocity field of boundary layer flow over a rotating disk. The characteristics of velocity field at a fixed orbital angular section measured by a hot-wire anemometer show that the structure of the 3-dimensional boundary layer flow is deformed elliptically and displaced in a certain direction that is not in the orbital radial direction, but the direction of deformation depends on the combination of orbital and rotational directions. For coincide orbital and rotational directions, there are regions where the intensity of low-frequency disturbances increases rapidly in a certain central region (laminar region under pure rotation). The transient vortices, which form streaks on the coating film, are considered to be destroyed by low-frequency disturbances. However, for opposite orbital and rotational directions, the low-frequency disturbances are not observed in any section. As the adding orbital speed increases, the intensity of velocity fluctuations in the turbulence region becomes larger in the expected except in a certain region. This location of the region also depends on the direction of deformation or the combination of orbital and rotational directions.

晶粒尺寸对界面含Cr-O-C防黏层Cu/Ni复合体拉伸性能的影响

通过分子动力学方法研究含Cr-O-C防黏层的具有不同晶粒尺寸的Cu/Ni复合体的拉伸变形。结果表明:当Cu/Ni复合体的晶粒尺寸大于12 nm时,不论界面不含Cr、O和C原子或含有定量Cr、O和C原子,复合体的屈服强度随着晶粒尺寸的减小呈现增大趋势,符合细晶强化规律,晶粒塑性变形主要受晶体内部的位错滑移控制,最大应力增加9.52%;当晶粒尺寸小于12 nm时,由于晶界所占比例的增加,拉伸过程的塑性变形更多受晶界变形控制,屈服强度下降。Cr-O-C界面弱化了Cu/Ni复合体的强度,随着界面上Cr、O和C原子数量的增加,Cu/Ni复合体的抗拉强度随之降低,最大应力下降56.40%,Cu/Ni复合体内部的位错数量也随之降低,转移到Ni表面的Cu原子数量随之减少。

Ag_(2)O-NiTi-LDH复合材料的构建及其光催化氧化乙硫醇性能研究

本文将氧化银(Ag_(2)O)负载到镍-钛层状双金属氢氧化物(NiTi-LDH)上以构建Ag_(2)O-NiTi-LDH复合材料。通过XRD、SEM、TEM、XPS、UV-vis、电化学工作站和FT-IR等技术对样品进行表征。采用静态吸附-光催化的方法对乙硫醇进行吸附氧化降解。结果表明:复合材料中Ag_(2)O和NiTi-LDH之间存在相互作用,使得Ag_(2)O-NiTi-LDH复合材料比单一基体材料的带隙能小,光生电子-空穴的分离和迁移效率高;在光催化实验中,单一的基体材料NiTi-LDH对乙硫醇的光催化效果不明显,Ag_(2)O和Ag_(2)O-NiTi-LDH虽然都能将乙硫醇光催化氧化成硫酸盐,但Ag_(2)O-NiTi-LDH复合材料光催化氧化降解效率高于Ag_(2)O。

Numerical investigations of asymmetric flow of a micropolar fluid between two porous disks

Numerical solution is presented for the two- dimensional flow of a micropolar fluid between two porous coaxial disks of different permeability for a range of Reynolds number Re （-300≤ Re 〈 0） and permeability parameter A （1.0≤A ≤2.0）. The main flow is superimposed by the injection at the surfaces of the two disks. Von Karman＇s similarity transformations are used to reduce the governing equations of motion to a set of non-linear coupled ordinary differential equations （ODEs） in dimensionless form. An algorithm based on the finite difference method is employed to solve these ODEs and Richardson＇s extrapolation is used to obtain higher order accuracy. The results indicate that the parameters Re and A have a strong influence on the velocity and microrotation profiles, shear stresses at the disks and the position of the viscous/shear layer. The micropolar material constants cl, c2, c3 have profound effect on microrotation as compared to their effect on streamwise and axial velocity profiles. The results of micropolar fluids are compared with the results for Newtonian fluids.

Plasma-Assisted ALD of an Al_2O_3 Permeation Barrier Layer on Plastic

Atomic layer deposition （ALD） technique is used in the preparation of organic/inorganic layers, which requires uniform surfaces with their thickness down to several nanometers. For film with such thickness, the growth mode defined as the arrangement of clusters on the surface during the growth is of significance. In this work, Al2O3 thin film was deposited on various interfacial species of pre-treated polyethylene terephthalate （PET, 12 μm） by plasma assisted atomic layer deposition （PA-ALD）, where trimethyl aluminium was used as the Al precursor and O2 as the oxygen source. The interracial species, -NH3, -OH, and -COOH as well as SiCHO （derived from monomer of HMDSO plasma）, were grafted previously by plasma and chemical treatments. The growth mode of PA-ALD Al2O3 was then investigated in detail by combining results from in-situ diagnosis of spectroscopic ellipsometry （SE） and ex-situ characterization of as-deposited layers from the morphologies scanned by atomic force microscopy （AFM）. In addition, the oxygen transmission rates （OTR） of the original and treated plastic films were measured. The possible reasons for the dependence of the OTR values on the surface species were explored.

In-situ formation of Li_(0.5)Mn_(0.5)O coating layer through defect controlling for high performance Li-rich manganese-based cathode material

Li-rich layered oxide of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)(LMNO)with a considerable specific capacity and higher voltage is regarded as a kind of promising cathode material.However,it suffers from transition metal ion dissolution and oxygen escape that leads to rapid capacity decay.In addition,the poor lithium-ion diffusion kinetics gives rise to unsatisfied rate performance.Herein,a stable layer of Li_(0.5)Mn_(0.5)O(LMO)out of LMNO is in-situ constructed through acetic passivation and following calcination process.The generated defect structure in the composite material exhibits fast ion diffusion kinetics and the produced LMO layer can stabilize the substructure,resulting in elevated cycling stability and rate performance.In specific,the LMNO@LMO material exhibits a high initial coulombic efficiency of 80.3%and remarkable capacity retention of 80.7%after 200 cycles at 1 C.Besides,the composite material reveals prominent rate performance that delivers discharge capacities of 158 and 131 m Ah g^(-1) at 5 and 10 C,respectively.At last,this study presents a new approach to optimizing the Li-rich cathode materials.

Effect of Al_2O_3 Buffer Layers on the Properties of Sputtered VO_2 Thin Films

VO_2 thin films were grown on silicon substrates using Al_2O_3 thin films as the buffer layers. Compared with direct deposition on silicon, VO_2 thin films deposited on Al_2O_3 buffer layers experience a significant improvement in their microstructures and physical properties. By optimizing the growth conditions, the resistance of VO_2 thin films can change by four orders of magnitude with a reduced thermal hysteresis of 4 °C at the phase transition temperature. The electrically driven phase transformation was measured in Pt/Si/Al_2O_3/VO_2/Au heterostructures. The introduction of a buffer layer reduces the leakage current and Joule heating during electrically driven phase transitions. The C–V measurement result indicates that the phase transformation of VO_2 thin films can be induced by an electrical field.

Influences of different oxidants on characteristics of La_2O_3/Al_2O_3 nanolaminates deposited by atomic layer deposition

A comparative study of two kinds of oxidants（H2O and O3） with the combination of two metal precursors（TMA and La（～iPrCp）3） for atomic layer deposition（ALD） La2O3/Al2O3 nanolaminates is carried out. The effects of different oxidants on the physical properties and electrical characteristics of La2O3/Al2O3 nanolaminates are studied. Initial testing results indicate that La2O3/Al2O3 nanolaminates could avoid moisture absorption in the air after thermal annealing. However, moisture absorption occurs in H2O-based La2O3/Al2O3 nanolaminates due to the residue hydroxyl/hydrogen groups during annealing. As a result, roughness enhancement, band offset variation, low dielectric constant and poor electrical characteristics are measured because the properties of H2O-based La2O3/Al2O3 nanolaminates are deteriorated. Addition thermal annealing effects on the properties of O3-based La2O3/Al2O3 nanolaminates indicate that O3 is a more appropriate oxidant to deposit La2O3/Al2O3 nanolaminates for electron devices application.

Uniform AlF_3 thin layer to improve rate capability of LiNi_(1/3)Co_(1/3) Mn_(1/3)O_2 material for Li-ion batteries

LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability.The samples were characterized by X-ray diffractometry (XRD),transmission electron microscopy (TEM),energy dispersive spectroscopy (EDS),charge-discharge cycling,cyclic voltammetry (CV),and electrochemical impedance spectroscopy (EIS).Uniform coated layer with a thickness of about 3 nm was observed on the surface of LiNi1/3Co1/3Mn1/3O2 particle by TEM.At 0.5C and 2C rates,1.5% (mass fraction) AlF3-coated LiNi1/3Co1/3Mn1/3O2/Li in 2.8-4.3 V versus Li/Li+ after 80 cycles showed less than 3% of capacity fading,while those of the bare one were 16.5% and 45.9%,respectively.At 5C rate,the capacity retention of the coated sample after 50 cycles maintained 91.4% of the initial discharge capacity,while that of the bare one decreased to 52.6%.EIS result showed that a little change of charge transfer resistance of the coated sample resulting from uniform thin AlF3 layer was proposed as the main reason why its rate capability was improved obviously.CV result further indicated a greater reversibility for the electrode processes and better electrochemical performance of AlF3-coated layer.

Influence of annealing temperature on passivation performance of thermal atomic layer deposition Al_2O_3 films

Chemical and field-effect passivation of atomic layer deposition （ALD） Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy （TEM） and X-ray photoelectron spectroscopy （XPS）, respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.

Magnetic properties and structure of Ni_80Fe_20/Ni_48Fe_12Cr_40 bilayer films deposited on SiO_2/Si(100) by electron beam evaporation

Ni80Fe20/Ni48Fe12Cr40 bilayer films and Ni80Fe20 monolayer films were deposited at room temperature on SiO2/Si（100） substrates by electron beam evaporation. The influence of the thickness of the Ni48Fe12Cr40 underlayer on the structure, magnetization, and magnetoresistance of the Ni80Fe20/Ni48Fe12Cr40 bilayer film was investigated. The thickness of the Ni48Fe12Cr40 layer varied from about 1 nm to 18 nm while the Ni80Fe20 layer thickness was fixed at 45 nm. For the as-deposited bilayer films the introducing of the Ni48Fe12Cr40 underlayer promotes both the （111） texture and grain growth in the Ni80Fe20 layer. The Ni48Fe12Cr40 underlayer has no significant influence on the magnetic moment of the Ni80Fe20/Ni48Fe12Cr40 bilayer film. However, the coercivity of the bilayer film changes with the thickness of the Ni48Fe12Cr40 undedayer. The optimum thickness of the Ni48Fe12Cr40 underlayer for improving the anisotropic magnetoresistance effect of the Ni80Fe20/Ni48Fe12Cr40 bilayer film is about 5 nm. With a decrease in temperature from 300 K to 81 K, the anisotropic magnetoresistance ratio of the Ni80Fe20 （45 nm）/Ni48Fe12Cr40 （5 nm） bilayer film increases linearly from 2.1% to 4.8% compared with that of the Ni80Fe20 monolayer film from 1.7% to 4.0%.