THERMODYNAMIC ANALYSIS OF Mo-La_2O_3 THERMIONIC CATHODE WIRE

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THERMIONIC EMISSION OF CARBONIZED La-Mo CATHODE

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粉末粒度对SPS固相烧结La0.6Eu0.4B6阴极材料的影响

采用高能球磨法制备出La0 6Eu0.4B6纳米粉体,将球磨后的纳米粉进行放电等离子(SPS)烧结,制备出了高致密的La0.6Eu0.4B6多晶块体材料.系统研究了烧结温度、烧结压力对样品致密度和力学性能的影响.结果表明,该方法与传统热压烧结方法相比有效降低了烧结温度,制备出的样品密度、维氏硬度和抗弯强度分别达到4.71 g/cm3、23.37 GPa和295.14MPa,这些值均高于传统热压烧结方法.热电子发射结果表明,当阴极温度为1873 K时,最大发射电流密度为33.74 A/cm2.实验过程中还发现,在相同烧结工艺下,球磨纳米粉与粗粉相比,维氏硬度、抗弯强度和热电子发射电流密度分别提高了28％、58％和32％.因此,在固相烧结过程中,粉末粒度的减小,更有助于烧结性能的提高.     

La2O3对镦粗Mo棒的横向组织和塑性的影响

利用锻造镦粗工艺制备了高横向塑性的纯Mo和Mo-La2O3棒,检测了其在不同温度退火后的横向弯曲性能并观察了其组织结构。结果表明:纯Mo棒经锻造镦粗变形85%后横向具有较好的塑性,延伸率达到了5%;而同状态下的Mo-La2O3棒只有2%。这是因为此状态下纯Mo棒中的位错可动性要好。随着退火温度的升高,纯Mo棒和Mo-La2O3棒的横向塑性都逐渐升高,Mo-La2O3棒的最大横向延伸率大于纯Mo棒(超过10%)。Mo-La2O3棒横向塑性的提高与La2O3粒子钝化微裂纹有关。在退火过程中,镦粗纯Mo棒和Mo-La2O3棒都发生了回复再结晶过程,位错组态变化一致,镦粗过程中产生了大量位错胞,随着退火温度的升高而逐步消失。     

EFFECT OF La_2O_3 ON THE RECRYSTALLIZATION OF MOLYBDENUM WIRES

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Structure and electrochemical performance of spinel LiMn2O4 synthesized by mechanochemical process

1　INTRODUCTIONLithium ion battery was used in many areasbecause of its high voltage, high energy densityand long cycle life and so on. Spinel lithium man ganese oxide was one of the most promising mate rials in term of its environmental benign, low cost,easy preparation and temperature safety. Mainproblem is the poor cycle life. As we all know thatboth the structure and electrochemical performanceof material strongly depended on the preparingmethod and starting…     

La_2O_3-Mo阴极的发射机理

采用热分析、原位ＸＰＳ等方法对 Ｍｏ—Ｌａ２Ｏ３阴极中 Ｌａ的价态进行了研究,探讨了该阴极的发射机理．实验结果表明,在高温下Ｌａ２Ｏ３可以被Ｍｏ２Ｃ还原成单质Ｌａ． Ｌａ２Ｏ３－Ｍｏ阴极的发射可用原子膜机理解释：在阴极工作过程中,还原得到的 Ｌａ覆盖在Ｍｏ基体表面,降低了基体 Ｍｏ的逸出功,促进了阴极的发射根据此机理提出Ｌａ２Ｏ３－Ｍｏ电子管制备和运行工艺．使电子管的工作寿命提高到了满足实际应用要求的水平．     

A study on carburized La–Mo cathode material

The effect of carburization on the thermionic electron-emission properties of the La₂O₃-doped molybdenum (La–Mo) cathode has been systematically studied, and the optimal carburizing technology has been obtained. The optimal carburizing technology is that the La–Mo cathode is exposed to benzene vapour for 8 min at about 1500°C, and the pressure of benzene vapour is about 8.5–9.5 Pa. The thermionic electron-emission capacity of the La–Mo cathode has reached the level of the traditional thoriated tungsten (Th–W) cathode, and the service lifetime of the 6T51-type electron tube equipped with the La–Mo cathode has been about 1657 h under on–off working conditions. So it is possible that the La–Mo cathode will replace the Th–W cathode with the problems of radioactive pollution and drastic brittleness as cathode material of some powerful electron tubes, and this is also the purpose of the study.     

中低温用Sm1-2xEuxBaxB6阴极材料的制备及性能

采用硼/碳热还原-热压烧结集成工艺(BCTR&HP)制备了高纯致密的Sm_1-2xEu_xBa_xB₆(x=0.1,02,0.3)多晶块体,系统研究Eu&Ba掺杂SmB₆对其结构、力学性能与电学特性的影响。结果表明,BCTR&HP制备的Sm_1-2xEu_xBa_xB₆呈CsC1型简单立方单相结构,晶格常数随Eu&Ba掺杂量的增加而增大,贡献于力学性能的提高和电阻率的下降。热电子发射性能结果表明,Eu&Ba掺杂能够改善SmB₆阴极材料的发射特性,在测试温度1773 K,外加电压1 kV条件下,Sm_0.4Eu_0.3Ba_0.3B₆阴极的发射电流密度达到35.1 mA·cm^-2,零场电流密度达到21.4 mA·cm^-2,在1523~1773 K其平均有效功函数为3.6 eV,其固有的高电阻率可作为"直热式"阴极简化热子结构,具有很大的应用前景。     

Effect of surface free energy of acetylene black powder on air electrode performance

The effects of acetylene black powder surface free energy on air electrode electrochemical performance and lifetime were studied. The acetylene black was immersed in 30% H2O2 at room temperature and the changes of functional groups and surface free energy were investigated by X-ray Photoelectron Spectroscopy (XPS) and powder contact angle (CA). The air electrode performance was characterized by the potential polarization curves and the lifetime was measured by constant-current discharge. It shows that, its surface free energy is the lowest when the acetylene black is immersed in H2O2 for 240 h. The polarization potential of the air electrode prepared by the pretreated acetylene black is 0.25 V(vs. Hg/HgO), 0.21 V lower than the air electrode with untreated acetylene black when the working current density is 100 mA·cm-1 . And its lifetime is over 800 h at 80 mA·cm-1 . The pretreatment of acetylene black for proper time by H2O2 is favorable for the stability of the tri-phase reaction interface of air electrode and improvement of its performance.     

Effects of synthesis conditions on the structural and electrochemical properties of layered LiNi1/3Co1/3Mn1/3O2 cathode material via oxalate co-precipitation method

The uniform layered LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries was prepared by using (Ni1/3Co1/3Mn1/3)C2O4 as precursor synthesized via oxalate co-precipitation method in air. The effects of calcination temperature and time on the structure and electrochemical properties of the LiNi1/3Co1/3Mn1/3O2 were systemically studied. XRD results revealed that the optimal calcination conditions to prepare the layered LiNi1/3Co1/3Mn1/3O2 were 950°C for 15 h. Electrochemical measurement showed that the sample prepared under the such conditions has the highest initial discharge capacity of 160.8 mAh/g and the smallest irreversible capacity loss of 13.5% as well as stable cycling performance at a constant current density of 30 mA/g between 2.5 and 4.3 V versus Li at room temperature.     

INTERACTIONS BETWEEN La2O3 PARTICLES AND DISLOCATIONS IN Mo-La2O3 ALLOYS

1. Introduction Mo-La2O3 materials is a newly-developed high temperature structural materials which is widely used in electronics, chemistry and metallurgy industry, but also a novel thermionic electron-emmision materials for powerful electron tubes to re…     

热处理温度对镧钼丝组织与性能的影响

系统研究了纯钼丝和镧钼丝在不同温度下进行热处理后的组织与性能。结果表明，La2O3是镧在钼丝中的唯一存在形式，镧的添加，提高了丝材的室温强度和再结晶温度，改善了再结晶后的室温脆性，其综合性能明显高于纯钼丝。     

稀土镧钼热阴极材料表面镧元素的蒸发

从理论上计算了碳化Mo-La2O3热阴极材料在不同温度下活性物质镧元素的蒸发速度,分析了镧元素蒸发对材料热电子发射及其稳定性的影响.计算结果表明:当温度为1623～1700K时,阴极中镧的扩散速度大于阴极表面镧的蒸发速度,Mo-La2O3阴极表面单质La的生成和蒸发保持平衡,阴极发射稳定; 当工作温度超过1700K,阴极表面镧的蒸发速度超过扩散速度,发射电流逐渐减少.测试了Mo-La2O3阴极FU-6051电子管在不同温度时的发射性能,热力学理论计算结果较好地解析了实验结果.     

6T51高频加热电子管用碳化La2O3—Mo阴极的研究

研究了应用于6T51发射管中的碳化La2O3-Mo阴极的制作工艺及电子发射性能，在碳化钍钨阴极的实践基础上，实现了La2O3-Mo阴极的碳化以及碳化La2O3-Mo阴极6T51管的去气和阴极激活。对比碳化钍钨阴极，分析了碳化La2O3-Mo阴极6T51管的发射能力，认为目前碳化La2O3-Mo阴极研究的发射量最高水平只达到钝钨阴极的下限值，还不具备取代碳化Th-W阴极的条件，由于碳化Th-W阴极6T51管设计时所选取的阴极发射能力富余量相当大，经过严格的去气，老练处理，碳化La2O3-Mo阴极基本上满足6T51测试的要求，但其发射稳定性不好，发射寿命也不容易掌握，论述了La元素消耗或碳化层消耗是两个影响碳化La2O3-Mo阴极发射稳定性的因素。     

Finite difference model of thorium transport in tungsten

A finite difference model of thorium transport in tungsten electrodes and its effect on the thermionic emission current is presented. Lattice, grain boundary and surface diffusion, grain boundary and surface segregation, evaporation, limited solubility and the rate of formation of thorium metal from thorium oxide are included. From the view of thermionic emission, the “ideal” grain size depends on the operation temperature of the electrode. High operation temperatures (T > 2300 K) favor larger grain sizes. Low operation temperatures (T < 2000 K) favor smaller grain sizes. The emission current is sensitive to the prior thermal treatments that the electrode has seen.     

基于渐变孔隙正极和叉指型流道主动式锂空气液流电池电化学性能理论研究

提出了具有渐变孔隙正极结构的主动式锂空气液流电池,利用溶液泵驱动电解液循环,结合渐变孔隙正极结构,强化电极内部Li^+和O2扩散和结合能力,减弱电极钝化。基于COMSOL Multiphysics 5.3,建立二维电化学模型,用Darcy定律、Butler-Volmer方程和组分输运公式描述在渐变孔隙正极结构(ε=0.55+αX等)下电极内部电解液流动、正负极电化学反应及电解液中Li^+和O2浓度场分布。由于Li2O2积聚在正极孔隙内,电极比表面积下降,采用Carman-Kozeny方程修正渗透率K。研究渐变孔隙率、压强差、氧气参数、正极厚度及动力学速率系数对该电池放电性能影响。结果表明:在放电电流密度0.1 mA/cm^2,电池比电容量是被动式结构的2.5倍;与ε=0.85-0.1X相比,采用ε=0.55+αX结构的电化学性能较佳;在放电电流密度0.1 mA/cm^2下,正极厚度为500^750μm,电池放电性能较好。     

Ti4＋掺杂对Li2FeSiO4／C电化学性能的影响

用溶胶-凝胶法制备Ti4＋掺杂的Li2FeSiO4／C正极材料。用XRD、HRTEM和电化学方法研究了该材料的结构、形貌和电化学性能。结果表明,掺杂适量的Ti4＋不会改变Li2FeSiO4／C的正交晶系结构,可以稳定材料的结构,改善高倍率充放电性能。在室温下,Li2Fe0.97Ti0.03SiO4/C以0．1c倍率放电的首次放电比容量为149．1mA·h／g,20次循环后放电比容量为127．3mA·h／g,且不同倍率下的电化学性能明显优于未掺杂的Li2FeSiO4／C。交流阻抗谱研究表明,适量的Ti4＋掺杂,减小了正极材料在充放电过程中的电荷传递电阻,增加了材料的电子电导率,改善了材料的电化学性能。     

Synthesis and electrochemical characterization of layered Li[Ni1/3CO1/3 Mn1/3]O2 cathode material for Li-ion batteries

1 INTRODUCTIONDue to the high cost of LiCoO2,a commonlyused cathode material in commercial rechargeablelithium-ion batteries , much efforts have been madeto develop cheaper cathode materials than LiCoO2,Li Ni O2and Li MnO2have been studied extensivelyas possible alternatives to LiCoO2[1 4 ]. Stoichio-metric Li Ni O2is knownto be difficult to synthesizeandits multi-phase reaction during electrochemicalcyclingleads to structural degradation,andlayeredLi MnO2has a significant drawback…     

溶胶-凝胶法制备纳米复合Mo-La2O3阴极

采用溶胶-凝胶法制备出平均粒径小于60nm的Mo-La2O3粉末。将所制备出的纳米复合Mo-La2O3粉末经冷压、热压工艺后烧结成纳米复合Mo-La2O3阴极。发现用溶胶-凝胶法制备的Mo-La2O3阴极组织均匀，晶粒细小，La2O3粒子晶粒大多在100nm以下，且弥散分布在晶内及晶界上。在燃弧实验中发现用溶胶．凝胶法制备的纳米复合Mo-La2O3阴极击穿点分布存阴极表面的大部分面积上，烧蚀坑浅，且击穿优先发生在La2O3相上。