真空弧放电TiH合金阴极表面形貌分析

TiH合金电极是一种含氢量非常高的金属材料,用它作真空弧离子源的电极,可在真空环境下产生强度非常高的氢离子流。相比纯金属材料电极,TiH电极除了出现真空弧放电特有的融蚀现象外,还存在气体释放过程,所以它的表面形貌具有一定的独特性。利用扫描电子显微镜观察了单次放电和多次放电后阴极表面形貌,发现阴极斑在阴极表面微裂纹附近连续分布,气体释放生成很多小孔,使阴极斑区域呈絮状结构;弧流越大,阴极斑数量越多;多次放电后,阴极斑朝含氢量多的地方移动。该结果有助于了解含氢电极的真空弧放电过程,对该类放电的应用具有一定参考意义。     

真空热处理碳纳米管的储氢性能研究

研究了真空热处理对多壁碳纳米管(MWNTs)电化学储氢性能的影响.采用化学气相沉积法(CVD)制备碳纳米管，碳纳米管与LaNi₅储氢合金按质量比1∶10混合，制作成CNTs-LaNi₅电极.电解池采用三电极体系，6mol/L KOH为电解液，Ni(OH)₂为正极，Hg/HgO为参比电极.实验结果表明，在相同的充放电条件下，850℃时CNTs-LaNi₅电极的储氢性能最好，克容量最大为503.6mAh/g，相应的平台电压高达1.18V.从500—850℃随着温度升高，放电量有较大幅度的增加，但到950℃时放电量反而下降.由此可见，碳纳米管的热处理温度对碳纳米管的电化学储氢性能有着较大的影响. 关键词： 碳纳米管(CNTs) 储氢性能 5合金')" href="#">LaNi₅合金 化学气相沉积法(CVD法)     

The negative electrode development for a Ni–MH battery prototype

The negative electrode development for a nickel-metal hydride battery (Ni–MH) prototype was performed with the following procedure: (1) the Lm_0.95Ni_3.8Co_0.3Mn_0.3Al_0.4 (Lm=lanthanum rich mischmetal) intermetallic alloy was elaborated by melting the pure elements in an induction furnace inside a boron nitride crucible under an inert atmosphere, (2) the obtained alloy was crushed and sieved between 44 and 74 μm and mixed with teflonized carbon; (3) the compound was assembled together with a current collector and pressed in a cylindrical matrix. The obtained electrode presented a disc shape, with 11 mm diameter and approximately 1 mm thickness. The crystalline structure of the hydrogen storage alloy was examined using X-ray diffractometry. The measured hcp lattice volume was 1.78% larger than the precursor LaNi₅ intermetallic alloy, increasing the available space for hydrogen movement. Energy dispersive spectroscopy (EDS) and scanning electronic microscopy (SEM) measurements were used before and after hydriding in order to verify the alloy sample homogeneity. The negative electrode was electrochemically tested by using a laboratory cell. It activates almost totally in its first cycle, which is an excellent characteristic from the commercial point of view. The maximum discharge capacity reached was 314.2 mA h/g in the 10th cycle.     

Investigation of oxygen states and reactivities on a nanostructured cupric oxide surface

Nanostructured copper (II) oxide was formed on clean copper foil at room temperature using activated oxygen produced by RF discharge. CuO particles of approximately 10-20 nm were observed on the surface by Scanning Tunneling Microscopy (STM). The copper states and oxygen species of the model cupric oxide were studied by means of X-ray Photoelectron Spectroscopy (XPS). These oxide particles demonstrated abnormally high reactivity with carbon monoxide (CO) at temperatures below 100 °C. The XPS data showed that the interaction of CO with the nanostructured cupric oxide resulted in reduction of the CuO particles to Cu₂O species. The reactivity of the nanostructured cupric oxide to CO was studied at 80 °C using XPS in step-by-step mode. The initial reactivity was estimated to be 5 × 10⁻⁵ and was steadily reduced down to 5 × 10⁻⁹ as the exposure was increased. O1s spectral analysis allowed us to propose that the high initial reactivity was caused by the presence of non-lattice oxygen states on the surface of the nanostructured CuO. We established that reoxidation of the partially reduced nanostructured cupric oxide by molecular oxygen O₂ restored the highly reactive oxygen form on the surface. These results allowed us to propose that the nanostructured cupric oxide could be used for low temperature catalytic CO oxidation. Some hypotheses concerning the nature of the non-lattice oxygen species with high reactivity are also discussed.     

储氢材料与金属氢化物-镍电池

储氢合金是金属氢化物-镍电池的关键材料，文中简要评述了稀土镍系合金、Laves相系合金、镁基合金、钒基固溶体和纳米管材料作为储氢电极材料的研究进展与目前存在问题，并简要介绍了动力金属氢化物-镍电池的开发动态。     

Fabrication of nanoporous AuPt nanoparticles modified indium tin oxide electrode and their electrocatalytic effect

This paper describes the synthesis of nanoporous AuPt nanoparticles (np-AuPt NPs) by galvanic replacement reactions that involve large-sized silver nanoparticles (Ag NPs) electrodeposited upon an indium tin oxide (ITO) film glass as a sacrificial template. Compared to a previous synthetic route based on the formation and dealloying of Ag/Au alloy nanoparticles, this method can easily fabricate nanoporous Au nanoparticles (np-Au NPs), as well as nanoporous AuPt nanoparticles. Structural characterization indicated that the products had a particle size of ～170 nm with a ligament size of tens of nanometers. The fabricated np-Au NPs/ITO and np-AuPt NPs/ITO electrode were also tested and compared for the oxidation of hydrogen peroxide in a phosphate buffer solution (pH 7.0). The np-AuPt NPs/ITO electrode showed a much higher electrocatalytic efficiency and detection sensitivity to hydrogen peroxide than the np-Au NPs/ITO electrode.     

New layered metal oxides as positive electrode materials for room-temperature sodium-ion batteries

In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.     

Electrochemical properties of modified negative electrode for Ni-MH cell

This study discusses the influence of different composition of negative electrode material on the performance of Ni-MH cells. Two major groups of multicomponent alloys were used during the experiments: AB₅ and AB₂ types. The best capacity was observed for the AB₅-type alloy with the highest content of Co in its structure. The presence of Co in the alloy increased the capacity of the negative electrode most likely as a result of hydriding/dehydriding processes or Faradaic reaction following the dissolution-precipitation mechanism. The influence of different amounts of nickel (0–20 wt%) was determined. The presence of nickel in the electrode materials increased the current density as well as the diffusion of hydrogen into the bulk of alloys. Moreover, the carbon materials have been used as an additive for negative electrode grains in order to increase the conductivity and hydrogen sorption properties.     

表面修饰纳米TiO2的贮氢合金电极的光充电行为

采用水解-沉淀法制备了锐钛矿结构的纳米级TiO2,研究了表面修饰TiO2的贮氢合金电极的光充电、循环伏安及交流阻抗特性.结果表明,表面未修饰TiO2的贮氢合金电极在光照下电极电位基本无变化,而表面修饰TiO2的贮氢合金电极在光照下,电极电位向负方向偏移,可达-0.835V,表明在光照射条件下电极表面有氢原子形成.电化学阻抗谱的结果也表明,表面修饰电极在光照时表面有吸附氢存在,并存在氢原子向贮氢合金内部的扩散过程.扫描电镜观察表明,表面修饰TiO2的贮氢合金电极在光充电后产生的氢原子被贮氢合金吸收引起膨胀,导致表面出现大量微裂纹.     

含氢电极真空弧放电等离子体时空分布特性研究

真空弧离子源在真空镀膜、材料表面改性、真空大电流开关、加速器离子注入等领域有广泛应用,目前国内外对真空弧放电等离子体的研究主要针对纯金属或合金电极,对含氢电极的研究和公开报道较少.本文利用高时空分辨的四分幅图像诊断系统,结合氢和钛原子特征线单色器件,研究了含氢钛电极的真空弧微秒级脉冲放电等离子体的轴向和径向时空分布特性.研究表明:在真空击穿阶段,阳极区域发光更为明显,阳极电极解吸附释放的氢原子是引发击穿的主要放电介质;在真空弧阶段,阴极-绝缘-真空三结合点处产生圆锥状阴极斑,喷射出大量的等离子体以维持弧放电,同时电极内壁非阴极斑区域也有少量等离子体产生,等离子体中H原子的轴向和径向空间分布均比Ti原子均匀.     

An overview of progress in Mg-based hydrogen storage films

Mg-based hydrogen storage materials are considered to be one of the most promising solid-state hydrogen storage materials due to their large hydrogen storage capacity and low cost. However, slow hydrogen absorption/desorption rate and excessive hydrogen absorption/desorption temperature limit the application of Mg-based hydrogen storage materials.The present paper reviews the advances in the research of Mg-based hydrogen storage film in recent years, including the advantage of the film, the function theory of fabricating method and its functional theory, and the influencing factors in the technological process. The research status worldwide is introduced in detail. By comparing pure Mg, Pd-caped Mg, nonpalladium capped Mg, and Mg alloy hydrogen storage films, an ideal tendency for producing Mg-based film is pointed out,for example, looking for a cheap metal element to replace the high-priced Pd, compositing Mg film with other hydrogen storage alloy of catalytic elements, and so on.     

Features of the plasma saturation of nanocrystalline and coarse-crystalline titanium samples with hydrogen and deuterium

We investigate the laws governing the saturation of nano- and coarse-crystalline Ti-6Al-4V alloy samples with hydrogen from high-frequency and glow discharge plasmas with a view to finding materials suitable for making hydrogen accumulators. We conclude that nanocrystalline Ti-6Al-4V alloy holds promise for creating hydrogen accumulators, and hydrogen plasma of high-frequency discharge origin is a cleaner hydrogen saturation medium than that of non-self-sustained discharge origin.     

非晶态合金与氢相互作用的研究进展

非晶态合金在力学性能、耐磨耐蚀性、磁性等方面比传统晶态合金具有显著优势,是一类有优良应用前景的新型结构与功能材料.非晶态合金与氢相互作用可以产生很多有趣的物理化学现象和应用.本文从物理基础和材料应用两个方面评述非晶态合金和氢相互作用的研究进展,在物理基础研究方面,从氢在非晶态合金中的存在状态出发,讨论氢在非晶态合金中的溶解、分布、占位和扩散等相关物理问题,进而分析氢对非晶态合金的热稳定性、磁性、内耗、氢脆等的影响.在材料应用研究方面,对非晶态储氢合金、非晶态合金氢功能膜、吸氢改善非晶态合金的塑性和玻璃形成能力、氢致非晶化、利用非晶态合金制备纳米储氢材料等方面的研究进展进行评述.最后总结并展望有关非晶态合金与氢相互作用的研究和应用.     

Back discharge in multipoint-plane geometry in flue gases

The paper presents investigations of back discharge occurring in air and flue gases produced by the process of burning of liquefied petroleum gas or charcoal. The discharge was generated between a multineedle electrode and plate covered with fly ash layer. The aim of this work was to determine the effects of back discharge in multineedle-to-plate electrode configuration on the fly ash layer covering the plate electrode. Level of NO_x and CO emission was also measured. It was found that the chemical composition of flue gas can be changed in the domains where the back discharge occurs, for example, additional amounts of nitrogen oxides (NO and NO₂) are produced and also carbon oxide (CO) was produced at higher discharge current.     

An electrochemical and structural investigation of porous composite anode materials for LIB

A porous composite anode for lithium ion battery (LIB) was investigated. The composite anode was prepared by electrodepositing Sn?CSb alloy on a template-like electrode and then annealing it in the atmosphere of N₂, whereas the porous template-like electrode was obtained by forming a sponge-like porous membrane on a copper foil via a mixed phase inversion process, followed by pre-plating Cu through membrane pores in it. SEM and XRD results showed that composite structure of the anode consisted of electrodeposited Sn?CSb alloy dispersed in a PAN-pyrolyzed conjugated conducting polymer gridding, which was tightly connected with the Cu foil through transition alloy layer formed by heat treatment. Due to its relatively reasonable microcosmic structure, the composite anode presented better cycling performance and specific capacity retention during charging and discharging at diverse rates. When cycled between 0 and 2.0?V (vs Li/Li⁺) at 0.5?C rate, the reversible charge/discharge capacity of the composite material remained 415 and 414.8?mAh?g^?1, respectively, after 30 cycles, corresponding to 82.9% of the capacity retention. When charging and discharging at 2?C rate, the composite material electrode showed 71.7% capacity retention at the 30th cycle.     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

水中脉冲放电产生过氧化氢及其影响因素

采用介质涂覆的球-筒电极结构,用以脉冲电压条件下在水中产生放电,通过比色法检测放电产生的过氧化氢,研究了不同电压脉冲幅值、脉冲宽度(储能电容的大小)、水的电导率以及脉冲频率对过氧化氢产生速率的影响,实验结果表明过氧化氢的产率随电压脉冲幅值的增大而增大。当电压脉冲幅值足够高时,水中放电由流注放电形式转换为电弧放电形式,此时过氧化氢产率也大幅提高,而在相同电压条件下,随水的电导率的增大,过氧化氢的产率减小。在相同电压下,脉冲频率的增大,导致放电平均功率增大,水中放电产生过氧化氢的浓度提高。在3.3 W功率时,120 min后水中过氧化氢浓度达到0.2 mmol/L,从而证明了所用电极结构的优越性。     

Electrochemical hydrogen storage properties of melt-spun Ti0.9Zr0.1V0.2Ni1.5La0.5 alloy

The Ti_0.9Zr_0.1V_0.2Ni_1.5La_0.5 alloy samples were synthesized by melt-spinning technique at the different wheel velocity (cooling rate), and the structure and electrochemical hydrogen storage properties were investigated. The result indicated that the structure of the melt-spun ribbons mainly contains C14 Laves phase and V-based solid solution phase. The discharge capacity, cyclic stability, high-rate discharge ability and electrochemical kinetic of the alloy electrodes are correlated with the cooling rate (wheel velocity), and the maximum discharge capacity is over 200 mA·h/g at the wheel velocity of 20 m/s.     

Hydrogen storage in sonicated carbon materials

The hydrogen storage in purified single-wall carbon nanotubes (SWNTs), graphite and diamond powder was investigated at room temperature and ambient pressure. The samples were sonicated in 5 M HNO₃ for various periods of time using an ultrasonic probe of the alloy Ti-6Al-4V. The goal of this treatment was to open the carbon nanotubes. The maximum value of overall hydrogen storage was found to be 1.5 wt %, as determined by thermal desorption spectroscopy. The storage capacity increases with sonication time. The sonication treatment introduces particles of the Ti alloy into the samples, as shown by X-ray diffraction, transmission electron microscopy, and chemical analysis. All of the hydrogen uptake can be explained by the assumption that the hydrogen is only stored in the Ti-alloy particles. The presence of Ti-alloy particles does not allow the determination of whether a small amount of hydrogen possibly is stored in the SWNTs themselves, and the fraction of nanotubes opened by the sonication treatment is unknown. Received: 18 December 2000 / Accepted: 18 December 2000 / Published online: 9 February 2001