La0.7Mg0.3Ni3.4-x(Al0.3Co0.4)0.2+x(x=0~0.3)合金电极电化学性能研究

在氩气保护下,采用悬浮熔炼法制备La0.7Mg0.3Ni3.4（Al0.3Co0.7）x（x=0,0.2,0.4,0.6）储氢合金,用X射线衍射仪测试相组成,并用MDI Jade 5.0软件分析相组成和晶胞参数,用开口三电极法测试电极电化学性能。结果表明,合金相主要由LaNi5、LaMg2Ni9、La2Ni7和LaNi2.28相组成,随着合金中Al和Co含量的增加,合金放氢平台压下降,最大吸氢量为1.43%（x=0）,合金电极最大放电容量Cmax为381mA.h.g-1（x=0）,合金电极100个充放循环后的容量保持率S100从53.0%（x=0）增加到57.1%（x=0.3）,循环稳定性增强。当x=0.1时,合金电极的电化学动力学性能较好。     

Mg-50wt.%Ti_(1-x)C(x=0.1,0.2,0.3,0.4)合金的贮氢性能研究

采用机械合金化方法制备Mg-50wt.%Ti1-xCx(x=0.1,0.2,0.3,0.4)贮氢合金.x-射线衍射(XRD)分析结果表明,合金主要由Mg、Ti、c以及二元合金相Ti2C0.06和Mg2C3组成,随着球磨时间增加,合金的非晶化程度提高.压强-成分-温度(Pcr)测试结果显示,Mg-50wt.%Ti1-xC(x=0.1,0.2,0.3,0.4)合金的贮氢量分别为2.96、2.95、2.76、2.6wt.%;随着碳含量的增加,样品吸氢量逐渐减少,放氢温度和平台压也随之下降;适当增加球磨时间可降低吸放氢温度.     

Mo部分替代Ti对V_(40)Ti_(50)Fe_(10)合金储氢性能的影响

为了考察Mo部分替代Ti对高容量V_(40)Ti_(50)Fe_(10)合金储氢性能的影响,采用电弧熔炼制备了V_(40)Ti_(50-x)Mo_xFe_(10)(x=0～30)合金,系统地研究了该系列合金的结构和储氢性能随Mo替代Ti含量的变化规律,并探讨合金储氢容量的衰退机制。研究表明:该系列合金均由主相体心立方(BCC)固溶体和少量的C14型Laves第2相组成;Mo取代Ti并未改变合金的主相结构,但Laves第2相的含量明显降低,合金整体均匀性增加;随着Mo含量的增加,BCC相的晶胞体积逐渐减小,合金的放氢量总体呈现下降趋势但中间出现波动状态,而放氢平台压则持续上升;在这一系列合金中,V_(40)Ti_(40)Mo_(10)Fe_(10)合金的储氢性能较优,具有相对宽泛且平坦的放氢压力平台,可逆储氢量较高,且室温下吸放氢过程均可在5 min内完成。循环测试表明,合金氢化物在吸放氢过程中会形成难以活化的TiFe相,导致合金出现成分分离,影响合金的稳定性,从而造成储氢容量衰退。     

Zr-Hf-Co合金储氢性能研究

研究了Hf部分替代Zr对Zr-Hf-Co合金储放氢性能的影响,结果表明:Zr-Hf-Co合金保持原始Zr-Co合金单一的立方相结构,且Hf含量变化对合金晶胞体积影响不大;随Hf替代量增加,Zr-Hf-Co合金的放氢平台压升高,100 kPa平衡放氢压力对应的放氢温度显著降低,由Zr-Co合金的673 K降低到Zr0.7Hf0.3Co合金的618 K;热力学计算结果得到Zr-Hf-Co合金的放氢反应焓变ΔH随Hf替代量增加而降低,表明Zr-Hf-Co合金氢化物的稳定性降低,有利于合金在较低温度下放氢;合金的最大吸氢量随Hf替代量增加而略有降低,但吸氢动力学性能变化不明显.     

TiFe基储氢合金的BaZrO3坩埚熔炼制备及其储氢性能

利用自制25 kg 级BaZrO3坩埚,通过ZG-0．05型真空感应熔炼制备 TiFe 基储氢合金。熔炼条件为：0．6 MPa氩气保护气氛,精炼时间5～10 min,精炼温度1450℃左右。采用ICP原子发射光谱分析仪分析所熔合金的化学成分,利用金相显微镜、扫描电子显微镜、XRD 衍射仪研究了合金的金相组织、表面形貌、微区元素分布、物相结构,用气体反应控制器测定了合金的PCT曲线。研究表明：由BaZrO3坩埚熔炼的TiFe基储氢合金氧质量分数与石墨坩埚熔炼的合金氧质量分数均小于0．1％,而石墨坩埚熔炼的合金碳质量分数为0．417％。BaZrO3坩埚熔炼后的合金完全由等轴晶构成,而石墨坩埚熔炼后的合金则由等轴晶组织和在晶粒内或沿晶界分布的球形TiC颗粒组成。BaZrO3坩埚所熔炼的合金不仅最大吸氢量比石墨坩埚熔炼的合金的最大吸氢量大,而且吸放氢平台压力也低。     

NdFeB磁性材料化学镀非晶态Ni—W—P合金及其相转变行为

采用化学镀方法在NdFeB磁性材料表面施镀非晶态Ni—W—P合金,利用扫描电子显微镜（SEM）及X射线衍射仪对Ni—WP合金镀层的组织形貌、结构及其相转变行为进行了分析．结果表明,非晶态Ni—W—P合金镀层是由大量不同尺寸的颗粒状或胞状突起组成,随着热处理温度逐渐升高,镀层结构由非晶结构逐渐转变为晶态结构,非晶态Ni—W—P合金镀层的晶化转变温度范围为350～380℃．     

LaNi_(2.5)Co_(0.5)储氢合金在充放电循环过程中的电化学性能研究

以感应熔炼法制备的LaNi_(2.5)Co_(0.5)合金为研究对象,对该合金及其氢化物的相结构进行了分析,并对合金电极的放电容量保持率、高倍率放电性能、氢扩散系数及极化电流密度等电化学性能进行了研究.结果表明:吸氢后的合金会产生明显的非晶化现象,造成合金吸放氢能力和氢化物稳定性下降.随着循环次数的增加,合金的放电容量和高倍率放电性能均表现出先快速下降到逐渐缓慢降低的趋势,而合金的氢扩散系数和极化电流密度却呈现出不同的变化趋势.高倍率放电性能的下降主要与合金表面反应活性相关,说明表面劣化现象是造成合金电化学性能衰退的主要因素.     

Nb对TiV0．9Cr1．3合金贮氢性能的影响

研究Nb对TiV0.9Cr1.3合金贮氢性能的影响,结果表明,TiV0.9-xCr1.3Nbx合金为单相bcc结构,铸态呈树枝晶状组织,当x＞0.3时,出现少量的Laves(Cr2Nb)结构相,并且树枝晶的二次枝晶消失了.随着x从0增加到0.4,合金的晶格常数变大,放氢平台压力、吸放氢量降低,但是放氢平台变得平坦.放氢平台斜率从1.59降到0.71,且氢化物生成焓、熵绝对值增大.TiV0.6Cr1.3Nb0.3合金最大贮氢量质量分数w为3.254%,有效贮氢量为2.367%,平台压为0.09 MPa,放氢平台斜率为1.0.     

V-Ti-Cr系储氢合金吸氢动力学机制研究

通过试验测试及动力学方程计算,研究了(TiCr)1-xVx(x=0.05,0.10,0.35)V-Ti-Cr系合金吸氢动力学机制.结果显示,随着钒含量的增加,合金由莱维氏单相结构逐渐转变为莱维氏相和低钒含量的体心立方(BCC)固溶体两相结构,最终转变为高钒含量的BCC固溶体单相结构.相应地,其吸氢机制也由化学反应控制,逐渐转变为形核长大机制,最终转变为三维扩散机制.相结构的变化同吸氢机制的变化有一定的对应关系,吸氢动力学机制不同,表现出吸氢速率不同,化学反应控制的吸氢过程速度较快,三维扩散机制控制的吸氢过程速度较慢.     

LaNi_（5－x）Al_x贮氢合金的研究

用Ａｌ置换ＬａＮｉ５贮氢合金中部分Ｎｉ，得到一系列ＬａＮｉ（５－ｘ）Ａｌｘ（ｘ＝０．１，０．３，０．５）贮氢合金．通过对合金的热力学性能的测试可知：随着Ａｌ的加入及其含量的增加，贮氢合金的平台氢压降低，吸氢量有所减少，而吸氢速度有所增加．通过对合金及吸氢后氢化物品体结构的Ｘ射线衍射分析，发现Ａｌ的加入并未使晶体结构类型发生变化，只是晶格常数略有增加；同时还证明了ＬａＮｉ（５－ｘ）Ａｌｘ合金吸氢后其晶体结构也未发生变化，但晶格常数增加较大．     

Hydrogen storage performance of LaNi3.95Al0.75Co0.3 alloy with different preparation methods

Rare-earth AB₅-type La–Ni–Al hydrogen storage alloys are widely studied due to their extensive application potentials in hydrogen isotope storage, hydrogen isotope isolation and hydrogen compressors, etc. Good hydriding/dehydriding kinetics, easily activation, high reversibility are important factors for their practical application. However, their overall hydrogen storage performance, especially plateau pressure and hydrogen absorption/desorption durability need to be further optimized. In this study, the microstructures and the hydrogen storage properties of as-cast, annealed, and melt-spun LaNi_3.95Al_0.75Co_0.3 alloys were investigated. The experimental results of XRD and SEM showed that all alloys contained a pure CaCu₅ type hexagonal structure LaNi₄Al phase. The cell volume increased in an order of annealed ?> ?melt-spun ?> ?as-cast, resulting in a lower hydrogen absorption/desorption plateau pressure and a more stable hydride phase. The hydrogen storage capacity of three alloys was almost the same. The slope factor of the annealed and melt-spun alloys is smaller than the as-cast alloy, indicating that heat-treatment process can make the alloys more uniform. For the cycle stability of the alloys, the hydrogen absorption rate of the annealed alloy and melt-spun alloy was much faster than that of the as-cast alloy after 500 cycles. The melt-spun alloy showed high pulverization resistance during hydrogen absorption/desorption, and exhibited an excellent cycling retention of 99% after 500 cycles, suggesting that melt-spinning process can enhance the cycle stability and improve the cycle life of the alloy.     

添加硼对La-Mg-Ni系(PuNi3-型)贮氢合金微观结构及电化学性能的影响

为了提出La-Mg-Ni(PuNi3型)系贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中添加微量的B,用铸造及快淬工艺制备La2Mg(Ni0.85Co0.15)9Bx(x=0,0.05,0.10,0.15,0.20)贮氢合金,分析测试铸态及快淬态合金的微观结构与电化学性能,研究硼对合金微观结构及电化学性能的影响。结果表明:铸态合金具有多相结构,包括主相(La,Mg)Ni3相(PuNi3型)和LaNi5相,一定量的LaNi2相和微量的Ni2B相经快淬处理后,Ni2B相消失,且其他相的相对量随淬速的变化而变化。硼的加入提高了铸态及快淬态合金的循环稳定性,但使铸态合金的容量下降;铸态合金的电化学容量随B含量的增加单调下降,而快淬态合金的容量随B含量的增加有一极大值,B对铸态及快淬态合金电化学性能的影响机理是完全不同的。     

Hydrogen absorption behavior of TA15 alloy

The hydrogen absorption kinetics of TA15 titanium alloy at 973–1123 K was studied using a tube-type hydrogen treatment furnace. The hydrogen absorption kinetic curves obtained were analyzed according to a series of mechanism equations to reveal the kinetic parameters and mechanism of the hydrogen absorption process. The results show that both the hydrogen absorption rate and the equilibrium hydrogen pressure increase and the time to reach equilibrium is shortened with increasing temperature. It is found that only the second hydrogen absorption period exists in the hydrogen absorption process of TA15 alloy between 973 and 1123 K, and the activation energy is 54.889 kJ/mol for hydrogen absorption. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results demonstrate that δ hydride forms between 973 and 1123 K, and β phase decreases with the increase of temperature. Orthorhombic α″ martensite is generated at 1073-1123 K, and their amount increases with increasing temperature.     

添加Ti0.9Zr0.1Mn1.5复合球磨对Ti9.6V86.4Fe4 合金储氢性能的影响

系统研究了Ti9.6V86.4Fe4储氢合金中掺入10%（质量分数）的Ti0.9Zr0.1Mn1.5进行复合球磨对其相结构及储氢性能的影响.X射线衍射分析表明,Ti9.6V86.4Fe4铸态合金具有单一的体心立方（BCC）结构固溶体相,当添加10%的Ti0.9Zr0.1Mn1.5复合球磨后,复合物由BCC主相和C14型Laves第2相组成.扫描电子显微镜及X射线能量色散谱仪分析表明,Ti9.6V86.4Fe4合金粉颗粒表面包覆了一层Ti0.9Zr0.1Mn1.5微粒.储氢性能测试表明,Ti9.6V86.4Fe4中掺入10%的Ti0.9Zr0.1Mn1.5复合球磨后,虽然室温最大吸氢量（质量分数）从3.86%略微降低至3.61%,但其有效储氢量（质量分数）由2.01%提高到2.11%,活化性能和P-C-T曲线平台特性都得到了明显改善.     

Effect of heat treatment on hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy

Effect of heat treatment on the crystal structure, microstructure, hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy prepared by arc-melting was studied in this work. It was found that both the as-cast and annealed (973 K/72 h) V68Ti20Cr12 alloys consisted of a single body-centered cubic (bcc) phase. After heat treatment, the hydrogen absorption/desorption kinetic characteristics of the as-cast alloy was improved greatly due to the homogeneous composition and perfect structure. The mechanism of hydrogen absorption/desorption process in the as-cast and annealed alloys was further investigated according to the Johnson-Mehl-Avrami (JMA) equation. The hydrogen absorption process of the as-cast and annealed alloys would be controlled by the one-dimensional diffusion process, while the hydrogen desorption process in the as-cast and annealed alloys was dominated by the geometrical contraction model. The pressure-composition-temperature (PCT) measurements show that the plateau pressure of the annealed alloy becomes comparatively flat. Furthermore, the activation energies of the dehydrogenation in the as-cast and annealed alloys were calculated using the Kissinger method, indicating that heat treatment is a very beneficial way to improve hydrogen absorption/desorption kinetics of the alloy.     

快淬Mg2Ni型合金的结构及贮氢动力学

用快淬技术制备Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金,用XRD,SEM和HRTEM分析合金的微观组织结构;测试合金的气态及电化学贮氢动力学。结果表明:快淬二元Mg2Ni合金具有典型的纳米晶结构,而快淬La替代合金明显地具有非晶结构,La替代Mg提高Mg2Ni型合金的非晶形成能力。La替代Mg明显地改变Mg2Ni型合金的相组成,当x=0.4时,合金的主相改变为(La,Mg)Ni3+LaMg3。快淬及La替代明显影响合金的气态及电化学贮氢动力学,La替代使合金的吸氢动力学先降低后增加,但使合金的气态脱氢及电化学贮氢动力学先增加后降低。快淬对合金气态及电化学贮氢动力学的影响与合金的成分相关,对于La0.4合金,合金的气态吸氢动力学随淬速的增加先增加后减小,其放氢动力学随淬速的增加而增加。     

La0.7Mg0.3-xCaxNi2.5Co0.5(x=0～0.15)储氢合金的放电容量衰退机理研究

采用感应熔炼结合粉末烧结两步法制备了La_(0.7)Mg_(0.3-x)Ca_xNi_(2.5)Co_(0.5)(x=0～0.15)储氢合金,并对合金的放电容量衰退机理进行了研究.研究结果显示随着Ca含量的增加,合金的相结构没有发生明显变化,只是晶胞参数逐渐增大,即Ca主要替代了超晶格结构AB2结构单元中的Mg,但在AB5结构单元中少量的Ca恰恰对合金的放电容量产生了重要的影响.Ca在AB2和AB5两种结构单元中的存在会降低储氢过程中晶胞内部的膨胀应力,Ca的溶解能够抑制Mg的腐蚀,生成微溶于水的腐蚀产物,并提高了合金表面具有催化活性的Ni含量,改善了合金的循环寿命.较高的Ca含量会严重破坏合金的相结构,生成过量的腐蚀产物因不能完全溶于水而在合金表面形成包覆层,阻碍了电极反应,造成合金循环过程中放电容量的急剧下降.     

Microstructural evolution and performance of hydrogen storage and electrochemistry of Co-added La0.75Mg0.25Ni3.5−xCox (x = 0, 0.2, 0.5 at%) alloys

Microstructure, hydrogen storage and electrochemical performances of Co-added La_(0.75)Mg_(0.25)Ni_(3.5_x)Co_x(x = 0,0.2, 0.5 at%) alloys are studied. XRD and rietveld refinement results suggest that the samples are mainly composed of(LaMg)Ni_3,(LaMg)_2Ni_7 and LaNi_5 phases, Co substitution for Ni changes the phase abundance,but not the phase composition. With the rising of Co content, the amount of(LaMg)_2 Ni_7 phase decreases, but the amount of LaNi_5 phase increases, while the amount of(LaMg)Ni_3 phase firstly increases and then decreases.The alloys reversibly absorb and desorb hydrogen at 298 K smoothly. When Co content is 0.2 at%, the hydrogen absorption capacity reaches the maximum value of 1.14 H/M, and the absorption capacities reach 1.09 H/M and 1.03 H/M in the first minute at 298 K and 323 K, respectively. Electrochemical performance measurement results show that La_(0.75)Mg_(0.25)Ni_(3.5-x)Co_x alloys are completely activated within 2 cycles, and the cyclic stability of La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy approaches 63.7% after 100 charge/discharge cycles, which is higher than that(S_(100) = 60%) of La_(0.75)Mg_(0.25)Ni_(3.0)Co_(0.5) alloy. Thus, the La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy exhibits optimum comprehensive properties of hydrogen storage and electrochemistry.     

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-Mn_0.30Al_0.30)_x (x=0.68, 0.70, 0.72, 0.74, 0.76) alloys and Cu-substituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-y Cu_y Mn_0.30Al_0.30)_0.70 (y=0, 0.10, 0.30, 0.50) alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi₅ phase, a LaNi₃ phase, and a minor La₂Ni₇ phase; in addition, in the case of Cu-substitution, the Nd₂Ni₇ phase appears and the LaNi₃ phase vanishes. Thermodynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with increasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ameliorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.