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.

Direct Synthesis of Al_2O_3-modified Li(Ni_(0.5)Co_(0.2)Mn_(0.3))O_2 Cathode Materials for Lithium Ion Batteries

To improve the cyclic stability at high temperature and thermal stability, the spherical Al2O3-modified Li（Ni0.5Co0.2Mn0.3）O2 was synthesized by a modified co-precipitation method, and the physical and electrochemical properties were studied. The TEM images showed that Li（Ni0.5Co0.2Mn0.3）O2 was modified successfully with nano-Al2O3. The discharge capacity retention of Al2O3-modified Li（Ni0.5Co0.2Mn0.3）O2 maintained about 99% after 200 cycles at high temperature（55 ℃）, while that of the bare one was only 86%. Also, unlike bare Li（Ni0.5Co0.2Mn0.3）O2, the Al2O3-modified material cathode exhibited good thermal stability.

ASTUDY OF VALENCE OF YTTRIUM IN Y_2O_3 Mo CATHODE

The valenceofelementyttrium of Y2 O3 Mocathode materialhasbeenstudied by usingther mal weight analysis, X ray diffraction analysis, Scanning electron microscopy and X rayphotoelectronspectrum . It hasbeen provedthatyttrium oxidecan bereduced by molybdenum carbide. Thereaction between powdered Y2 O3 and Mo2 Ccan happen at 1173 , and Y2 O3may bereduced to metallicyttrium . Afterthepowder mixtureof Y2 O3 and Mo2 Cwasheat treated at1873 K, Yttrium existsin two kinds of chemicalstate- yttrium of zero valence and yttrium ofthreevalences.

Synthesis of Y_2O_3:Eu^(3+) phosphors by surface diffusion and their photoluminescence properties

Y2O3:Eu3+ phosphors were synthesized by the surface diffusion method (SDM). X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS) were used to characterize the structure, morphology and component of Y2O3:Eu3+ phosphors. The photoluminescent (PL) properties were also investigated. The results reveal that the PL intensity of Y2O3:Eu3+ phosphors prepared by the surface diffusion method (SDM) is much higher than that prepared by homogeneous co-precipitation. The luminescence efficiency of the sample (Y0.997, Eu0.003)2O3 prepared by the SDM is almost 1.9 times that by homogeneous co-precipitation. The concentration of Eu3+ in the phosphor Y2O3:Eu3+ prepared by the surface diffusion can be reduced greatly owing to the activator, Eu3+ ions, distributing mainly in the outer layer of the phosphors where the photon generation process occurs.

Chemical stability of La_2O_3 in La_2O_3-Mo cathode materials

Chemical stability of La 2O 3 in carbonized and uncarbonized La 2O 3 Mo cathodes was studied by in situ XPS analysis. Experimental results show that chemical stability of La 2O 3 is not good enough. In vacuum and at high temperature, oxygen can be dissociated from the lattice of La 2O 3 in the uncarbonized La 2O 3 Mo cathode. Binding energy shifts of La?3d5/2 and La?3d3/2 core peaks, and obvious decrease of satellite peak intensity in La?3d doublet with increasing temperature show that metallic La appears at carbonized La 2O 3 Mo cathode surface at high temperature.

Emission mechanism of Mo-Y_2O_3 cathode

The valence of element yttrium of Y 2O 3 Mo cathode material was studied by thermal analysis, X ray diffraction analysis, scanning electron microscopy and X ray photoelectron spectra, and the emission mechanism of Mo Y 2O 3 cathode was discussed. It was proved that reaction between powder Y 2O 3 and Mo 2C can happen at 1 173 K, and Y 2O 3 be reduced to metallic yttrium. After the powder mixture of Y 2O 3 and Mo 2C is heat treated at 1 873 K, yttrium exists in two kinds of state—yttrium of zero valence and yttrium of three valences. The formation of monoatomic layer of metallic yttrium at the surface of filament is the cause of emissivity of the cathode. Yttrium at the surface doesn’t provide emission current, but the momoatomic active surface layer has a lower work function than clean molybdenum. [

Theoretical studies of adsorption property on Ir_4/MgO and Ir_4/γ-Al_2O_3

The adsorption properties of atomic and molecular species on Ir4/MgO and Ir4/γ-Al2O3 have been systematically studied by means of planewave density functional theory（DFT）calculations using the periodic boundary conditions.The binding energies of these species were ordered as follows：H2O〈C2H4〈H〈OH〈S〈N〈O〈C.The adsorption energies of adatoms on Ir4/MgO were larger than those on Ir4/γ-Al2O3 except hydrogen atom,but were in reverse for the molecules calculated.In addition,the difference of adsorption energies on MgO and γ-Al2O3 supports has been elucidated by analyzing the electronic properties.A detailed investigation on state density clarifies the nature of the magnitude of adsorption energy.These calculated results are consistent well with the available experimental and theoretical results.

Synthesis of Y_2O_3 particle enhanced Ni/TiC composite on TC4 Ti alloy by laser cladding

A Y2O3 particle enhanced Ni/TiC composite coating was fabricated in-situ on a TC4 Ti alloy by laser surface cladding. The phase component, microstructure, composition distribution and properties of the composite layer were investigated. The composite layer has graded microstructures and compositions, due to the fast melting followed by rapid solidification and cooling during laser cladding. The TiC powders are completely dissolved into the melted layer during melting and segregated as fine dendrites when solidified. The size of TiC dendrites decreases with increasing depth. Y2O3 fine particles distribute in the whole clad layer. The Y2O3 particle enhanced Ni/TiC composite layer has a quite uniform hardness along depth with a maximum value of HV1380, which is 4 times higher than the initial hardness. The wear resistance of the Ti alloy is significantly improved after laser cladding due to the high hardness of the composite coating.

Catalytic Performance and IR Characterization of Co-Mo/Al_2O_3 and Ru-Co-Mo/Al_2O_3 Catalysts in Hydrodesulfurization

Recently, owing to high costs and increasing demands for better catalysts, it is worthwhile to improve its activity and selectivity, and reduce its costs. Adding secondary promoters such as phosphorus, boron, magnesium, titanium, zinc and ruthenium to Co-Mo/Al;O;catalyst has been proved to be one of the ways to attain this result. The addition of those metals or metal oxides changes the surface states of molybdenumstructure.

In Situ IR Spectroscopic Study on the Hydrogenation of 1,3-Butadiene on Fresh Mo_2C/γ-Al_2O_3 Catalyst

The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.

High temperature cyclic oxidation behavior of Y_2O_3-ZrO_2 thermal barrier coatings irradiated by high-intensity pulsed ion beam

The high-temperature oxidation resistance behavior of 7% （mass fraction） Y203-ZrO2 thermal barrier coatings （TBCs） irradiated by high-intensity pulsed ion beam （HIPIB） was investigated under the cyclic oxidation condition of 1 050 ℃ and 1 h. The columnar grains in the TBCs disappear after the HIPIB irradiation at ion current densities of 100-200 A/cm^2 and the irradiated surface becomes smooth and densified after remelting and ablation due to the HIPIB irradiation. The thermally grown oxide （TGO） layer thickness of the irradiated TBCs is smaller than that of the original TBCs. After 15 cycles, the mass gains of the original TBCs and those irradiated by ion current densities of 100 and 200 A/cm^2 due to the oxidation are found to be 0.8-0.9, 0.6-0.7, and 0.3-0.4 mg/cm^2, respectively. The inward diffusion of oxygen through the irradiated TBCs is significantly impeded by the densified top layer formed due to irradiation, which is the main reason for the improved overall oxidation resistance of the irradiated TBCs.

Studies on the Hydrogenation of Acetonitrile over Fresh Mo_2C/γ-Al_2O_3 Catalyst by In-situ IR Spectroscopy

The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.

Tribological behavior and mechanism of NiCrBSi-Y_2O_3 composite coatings

The NiCrBSi-Y2O3 composite coatings were prepared on the surface of 45 carbon steel by plasma spray, the microstructure and tribological properties of the coatings were investigated. The results show that the NiCrBSi-Y2O3 composite coatings are mainly composed of γ-Ni, CrB, Cr7C3 and Y2O3. With addition of Y2O3, hard phases such as CrB, Cr7C3 emerge in composite coating, and the density of the composite coatings also increases. The NiCrBSi-0.5Y2O3 composite coating presents excellent tribological properties. Its friction coefficient is 0.175, which is about 37% of that of the pure NiCrBSi coating. The mass wear loss is 1.2 mg, which is reduced by 43% compared with the pure NiCrBSi coating. When the loads are 6-10 N, the NiCrBSi-0.5Y2O3 composite coating suffers from slight wear and the wear mechanisms are mainly adhesive wear accompany with slight micro-cutting wear and micro-fracture wear. As the load increases to 12 N, the wear mechanisms are adhesive wear and severe micro-cutting wear.

Y_(2)O_(3)含量对TC4表面WC增强钛基激光熔覆层组织与摩擦学性能的影响

目的增加航空TC_(4)合金的安全服役寿命。方法采用同轴送粉激光熔覆技术在其表面制备了TC_(4)+Ni-MoS_(2)+WC+xY_(2)O_(3)(x=0%、1%、2%、3%、4%,质量分数)耐磨复合涂层,利用着色渗透探伤、XRD、SEM、EDS、EBSD和TEM等多种检测手段和设备,分析了Y_(2)O_(3)添加对涂层组织与摩擦学性能的影响规律。结果3%Y_(2)O_(3)涂层的成形质量最优,所有涂层生成相相同,主要由TiC、Ti_(2)Ni、Ti_(2)S、基体β-Ti以及未熔WC组成。Y_(2)O_(3)与TiC、Ti_(2)S、Ti_(2)Ni之间形成了共格依附生长关系,所有涂层中均有效合成了TiC-Ti_(2)S、TiC-Ti_(2)Ni和Ti_(2)S-Ti_(2)Ni共格复合结构相。随着Y_(2)O_(3)含量增大,基体显露面积增加,其余物相逐步细化、团聚并沿晶界连续生长。所有涂层的显微硬度均高于TC_(4)基材,大小与Y_(2)O_(3)含量呈负相关变化。所有涂层的摩擦因数均高于基材,磨损率均低于基材,摩擦因数和磨损率随着Y_(2)O_(3)含量增加,出现了先降低后升高的变化规律,其中3%Y_(2)O_(3)涂层的摩擦因数最低(μ=0.4813),耐磨性(3.55×10^(4)mm^(3)/(N·m))和磨损面质量(Ra=21.24μm)最优。结论适量Y_(2)O_(3)有助于改善涂层的成形质量,Y_(2)O_(3)添加并未影响涂层物相种类,且可作为异质形核基底细化相互依附生长的TiC-Ti_(2)S-Ti_(2)Ni共格结构相,除基体相外,Y_(2)O_(3)易吸引其余物相在涂层晶界处钉扎;Y_(2)O_(3)含量增加不能增大涂层显微硬度,所有涂层均不具备减摩性能,但耐磨性均优于TC_(4)基材,适量Y_(2)O_(3)添加可使涂层综合摩擦学性能达到最优。

Ir在Pt/USY-Al2O3催化甲苯加氢反应中的开环效应

单环芳烃的加氢饱和选择开环是柴油深度脱芳过程中的重要反应.文采用浸渍法制得的Pt单活性组分和Pt-Ir的双活性组分与载体USY-Al2O3复配的两个系列的催化剂,研究了模型化合物甲苯的加氢转化反应规律.结果发现,活性组分Ir的引入,使得催化剂的开环性能有了明显地提高.

Interactions between γ-TiAl melt and Y_2O_3 ceramic material during directional solidification process

A γ-TiAl alloy with nominal composition of Ti-47%Al（molar fraction） was directionally solidified in an alumina mould with an Y2O3 protective coating.The effects of processing parameters（melting temperature and interaction time） on the metal-coating interface,microstructure and chemical composition of the alloy were evaluated.The result shows that the Y2O3 protective coating exhibits an effective barrier capability to avoid direct contact between the mould base material and the TiAl melt,although the Y2O3 coating is found to suffer some erosion and be slightly dissolved by the molten TiAl due to the coating-metal interactions.The directionally solidified alloys were contaminated with Y and O,and Y2O3 inclusions were dispersed in the metal matrix.The reason for this metal contamination is the Y2O3 coating dissolution by the TiAl melt.One mode of the interaction between Y2O3 and the TiAl melt is dissolution of yttrium and atomic oxygen in the melt by reaction Y2O3（s）=2Y（in TiAl melt）＋3O（in TiAl melt）.Both the extent of alloy contamination and the volume fractions of Y2O3 inclusions depend on the melting temperature and the interaction time.

Y_2O_3-Ir阴极的发射机理的研究

根据Ｙ２Ｏ３－Ｉｒ阴极研制过程中观察到的一些物理现象，结合扫描电镜对Ｙ２Ｏ３－Ｉｒ阴极表面化学成份分析的图谱，运用物理化学理论对该阴极的发射物质结合态进行研究．最后，在综合比较氧化物阴极的二种发射模型的基础上。

Solution combustion synthesis of Ni-Y_2O_3 nanocomposite powder

Ni-Y2O3 nanocomposite powder with uniform distribution of fine oxide particles in the metal matrix was successfully fabricated via solution combustion process followed by hydrogen reduction. The combustion behavior was investigated by DTA-TG analysis. The influence of urea to nickel nitrate（U/Ni） ratio on the combustion behavior and morphology evolution of the combusted powder was investigated. The morphological characteristics and phase transformation of the combusted powder and the reduced powder were characterized by FESEM, TEM and XRD. The HRTEM image of Ni-Y2O3 nanocomposite powder indicated that Y2O3 particles with average particle size of about 10 nm dispersed uniformly in the nickel matrix.

Effect of Y_2O_3 Content on Microstructure of Gradient Bioceramic Composite Coating Produced by Wide-Band Laser Cladding

To eliminate thermal stress and cracks in the process of laser cladding, a kind of bioceramic coating with gradient compositional design was prepared on the surface of Ti alloy by using wide-band laser cladding. And effect of Y2O3 content on gradient bioceramic composite coating was studied. The experimental results indicate that adding rare earth can refine grain. Different rare earth contents affect formation of HA and β-TCP in bioceramic coating. When the content of rare earth ranges from 0.4% to 0.6%, the active extent of rare earth in synthesizing HA and β-TCP is the best, which indicates that “monosodium glutamate” effect of rare earth plays a dominant role. However, when rare earth content is up to 0.8%, the amount of synthesizing HA and β-TCP in coating conversely goes down, which demonstrates that rare earth gradually losts its catalysis in manufacturing HA and β-TCP.

Hydrothermal synthesis of Y(OH)_3,Y(OH)_3:Eu^(3+) nanotubes and the photoluminescence of Y(OH)_3:Eu^(3+),Y_2O_3:Eu^(3+)

The phase and morphology transformation during the hydrothermal treating process of Y2O3 was evaluated with X-ray difference (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size and specific surface area determination. The results showed that the cubic Y2O3 did not transfer into hexagonal Y(OH)3 in pure water. Therefore, pure hexagonal Y(OH)3 with nanotube and microrod morphologies were obtained by hydrothermal treating Y2O3 at 150 oC for 12 h in 15 ml of 2 mol/L NaOH solution with and without PVA or PEG. It was suggested that the characteristic preferential growth of Y(OH)3 was attributed to the structure anisotropy of hexahedron Y(OH)3. The addition of PVA or PEG could promote the forming process of nanotubes by selective adsorption on different crystal planes, which altered the growth rate along different directions and resulted in the diffusion limit of constructing ions in the center top of rods. Finally, Y(OH)3:Eu and Y2O3:Eu nanotubes were also synthesized by using this method, and their photoluminescence properties were evaluated.