成分配比对稀土钨电极材料组织及力学性能影响

通过固液掺杂、等静压压制、中频烧结的方法，制备了不同的氧化镧、氧化钇、氧化锆三元掺杂成分比例的钨电极材料烧结棒材，探究了不同成分配比对样品显微组织、第二相粒子分布以及宏观力学性能的影响。结果表明，氧化镧、氧化钇、氧化锆三元复合添加能够有效改善第二相粒子在钨基体中的分布形态，降低第二相在晶界的过度富集，提高钨电极材料的综合力学性能。并且当添加成分镧、钇、锆质量比为3:1:1时，材料具有最好的综合力学性能，致密度可达96.04%，显微硬度可达549.37HV0.3，抗压强度可达3785MPa，原因是此配比下第二相粒子最为细小均匀，弥散程度最高，对基体晶粒的细化作用最好，该配比下钨基体平均晶粒尺寸达到10.3μm。     

Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

离子型稀土矿山淋洗及尾水富集试验研究

对浸矿后离子型稀土原地浸矿场采用清水进行淋洗，在184天的清水淋洗过程中，尾水氨氮值从最开始的507mg/L，降低至140mg/L，淋洗尾水pH4.52~3.10。淋洗尾水采用两级反渗透膜分离，既回收有价资源稀土，又能使出水氨氮达标。结果表明，产水氨氮浓度稳定低于15mg/L，对稀土的截留率高于98.25%，浓水中稀土离子平均浓度313.4mg/L，可进一步回收稀土资源。     

炼油废白土在水泥厂燃煤自备电厂中再利用的实践

本项目主要研究和实现了工业废白土在BAYAH燃煤自备电厂中的再利用,实现变废为宝,减少了环境污染,同时为企业创造了一定的经济效益。针对废白土的特性,对燃料输送系统给煤机、皮带机、煤仓、下料溜子和排渣系统进行了改造。通过修改操作规程消除废白土对锅炉运行的影响。     

Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

稀土石膏常压酸化法制备硫酸钙晶须的研究

以含稀土的石膏为原料运用常压酸化法合成硫酸钙晶须,探讨了不同工艺条件对生成的硫酸钙晶须形貌的影响,同时还考察了晶型助长剂的种类和晶型助长剂的含量对硫酸钙晶须生长的影响,利用SEM和XRD分别对硫酸钙晶须的表面形貌、物相特征做了表征分析。实验得到制备硫酸钙晶须的最佳的反应条件：稀土石膏质量浓度为0.22 g/mL、反应时间为25 min、盐酸浓度为2.8 mol/L、反应温度为70 ℃、陈化时间为4 h,在此条件下合成的硫酸钙晶须平均长度为61 μm,平均长径比为30.5;通过对比实验选出了CuCl₂作为促进硫酸钙晶须生长的助长剂,在添加5%（质量分数）的CuCl₂的情况下可使硫酸钙晶须长径比从30.5增至41,长度从61 μm增至81 μm。     

Energy storage performance of 0.55Bi0.5Na0.5TiO3-0.45SrTiO3 ceramics doped with lanthanide elements (Ln = La,Nd, Dy,Sm) using a viscous polymer processing route

Lead-free bismuth sodium titanate-strontium titanate (NBT-ST) dielectric ceramic materials have been extensively investigated energy storage materials because of their relaxor characteristics. In this study, four different lanthanide elements were introduced into the ferroelectric NBT-ST ceramic to improve their relaxor properties. The introduction of the lanthanide resulted in an increase in disorder at location A within the perovskite lattice and improved relaxor characteristics, leading to a stored energy density of more than 3.5 J/cm³. In particular, an ultrahigh recoverable stored energy density of 4.94 J/cm³ and efficiency of 88.45% were achieved at 440 kV/cm when the NBT-ST ceramic was modified with neodymium. The modified ceramic also exhibited good thermal stability in the range of 30–120 °C, as well as a fast discharge time of ～153 ns, indicating that Nd-incorporated NBT-ST is a promising candidate for electrical energy storage ceramic.     

Effect of sintering conditions on structural and morphological properties of Y- and Co-doped BaZrO3 proton conductors

BaZrO₃-based materials doped with a trivalent cation have excellent chemical stability and relatively high proton conductivity which makes them potential proton conducting oxide materials for various electrochemical device applications such as hydrogen processing, high-temperature electrolysis, and solid electrolyte in fuel cells. However, BaZrO₃ showed poor sinterability, requiring high sintering temperatures (1700–2100 °C) with longtime sintering (20–100 h) to achieve the desired microstructure and grain growth. This sintering problem can be solved by slightly doping BaZrO₃ with a sintering aid element. Therefore, in this study, two different zirconate proton conductors: BaZr_0·9Y_0·1O_3-α (BZY) and BaZr_0·955Y_0·03Co_0·015O_3-α (BZYC) were sintered in an air atmosphere and an oxygen atmosphere for 20 h in the temperature range of 1500–1640 °C. The sinterability was evaluated by analyzing the XRD diffraction patterns, lattice constant, lattice strain, crystallite size, relative density, open porosity, closed porosity, surface morphology, grain size, and grain boundary distribution, using the XRD, SEM, EDX, and Archimedes density measurement methods. It is concluded that in an oxygen atmosphere, sintering aid Co not only improves the relative density but also produces highly dense fine particles with clear grain boundaries which are promising for electrochemical hydrogen device applications.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.