Zr_(0.8)Ti_(0.2)(Ni_(0.6)Mn_(0.2)V_(0.2)Cr_(0.05))_x贮氢合金结构和电化学性能的研究

研究了Zr0.8Ti0.2(Ni0.6Mn0.2V0.2Cr0.05)x(x=1.8～2.4)贮氢合金中化学计量x对晶体结构和电化学性能的影响。结果表明:随着x值的增大,合金中C14相含量逐渐减少,C15相含量逐渐增加,C14和C15相的晶格常数均线性减小;随着x值的增大,合金电极的活化性能提高,高倍率放电性能和放电容量均先升高,至x=2.2时达到最大值(最大放电容量为370mAh/g);超化学计量合金电极的循环寿命随x值的增大而降低,但当x<2.2时,经充放电循环500次以后容量保持率仍在80%左右。当化学计量值x等于2.2时,合金电极的综合电化学性能最好。     

La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5-x)Fe_x系列合金的制备及其储氢性能

在制备La-Ni-Co-Fe中间合金的基础上,采用机械合金化方法制备La0.7Mg0.3Ni2.8Co0.5-xFex(x=0,0.1,0.2,0.3,0.4,0.5)系列储氢合金,研究在不同球磨时间下储氢合金的物相、微观形貌和电化学性能及元素置换对其储氢性能的影响。结果表明:La0.7Mg0.3Ni2.8Co0.5合金的主相为LaNi5相,La0.7Mg0.3Ni2.8Co0.5-xFex系列储氢合金球磨40 h和80 h后,主相为LaNi5相和少量LaMg2Ni9相;且随着球磨时间的增加,合金晶粒变细小,La0.7Mg0.3Ni2.8Co0.5合金的最大放电容量呈变大的趋势,从142.4 mA.h/g增加到157.5 mA.h/g,La0.7Mg0.3Ni2.8Co0.2Fe0.3合金的最大放电容量从150.7mA.h/g增加到162.1mA.h/g,合金具有较好的循环稳定性能。     

合金化对ZrMn2基Laves相贮氢合金相组成的影响

研究了Ni、V、Cr、Co、Fe、Cu和Ti等合金化元素取代ZrMn2 基Laves相贮氢合金的B侧或A侧对合金相组成的影响。结果表明 ,采用不同的元素对A侧或B侧进行部分取代 ,将引起ZrMn2 基合金相组成的变化。采用Ni取代Mn后 ,ZrMn2 合金的主相结构转变为C15型Laves相 ,表明Ni为C15相稳定元素。对Zr Mn Ni三元合金 ,V为C14相稳定元素 ,而Co、Fe、Cu则为C15相稳定元素。取代量较少时 ,Cr为C15相稳定元素 ,取代量增加时 ,C15相稳定作用减弱。Ti元素为C14相稳定元素 ,Ti对Zr的部分取代将导致合金主相结构转变为C14型Laves相。合金化元素对ZrMn2 合金的相组成的影响与元素的电子浓度和原子尺寸不同有关     

Structure and electrochemical performance of hydrogen storage alloy La0.7Mg0.3Ni2.875Co0.525Mn0.1-boron composite

The structure and electrochemical characteristics of La0.7Mg0.3Ni2.875Co0.525Mn0.1-boron composite was studied systematically. The AB3 type hydrogen storage alloys La0.7Mg0.3Ni2.875Co0.525Mn0.1 were successfully synthesized by means of inter-media alloy La2Mg17 . The alloys were composited with boron at different weight rate. From the XRD analyses, each alloy of this series is mainly composed of (La,Mg)Ni3 phase and the LaNi5 phase, and the phase abundance of each phase varies with the boron weight rate, moreover, after composition, the c and cell volumes of (La,Mg)Ni3 phase increase, and the LaNi5 phase keep the same, which indicate that the boron may enter (La,Mg)Ni3 phase. The electrochemical studies show that the maximum discharge capacity of the composites decreases, but the cycling life improved. And the high rate discharge ability and exchange impendence spectroscopy (EIS) of the AB3 alloys and its composite were also studied.     

Hydrogen storage properties of Laves phase Ti1-xZrx(Mn0.5 Cr0.5)2 alloys

The activation behaviors and hydrogen storage properties of the Laves phase Ti1-xZrx(Mn0.5Cr0.5)2(x=0,0.1,0.2,0.32,0.5) alloys were investigated by the pressure-composition-temperature (P-C-T) measurements. All the studied alloys show the single C14-type Laves phase structurebased on the XRD data. Except for the alloys with very low Zr content of x =0 and x =0.1, all these alloys can be fully activated. The P-C isotherms of the activated alloys show that, the introduction of Zr induces the decrease of the equilibrium pressures and the steeper plateaus. As the x increases, the maximum hydrogen absorption also increases, whereas the desorption of hydrogen decreases. These two effects result in a maximum reversible hydrogen storage capacity of H/M =3.03 for the alloy at x =0.32. Furthermore, the well-defined plateau associated with the smallest hysteresis also appears at x =0.32.     

低钴AB_5型贮氢合金的制备及电化学性能

为了降低镍氢电池的原材料成本 ,研究了一系列多元、低钴和无钴AB5型贮氢合金 ,以及取代元素对贮氢合金电化学性质的影响。结果显示 ,用少量的铁、铜和铬部分取代贮氢合金La(NiMnCoAl) 5中的钴对改善贮氢合金电化学循环稳定性有效。贮氢合金La(NiMnAl) 4.6(FeCuCr) 0 .2 Co0 .2 具有满意的循环稳定性 ,它在 0 .2C放电条件下的最大放电容量为 2 96mAh/g-1,经过 30 0次循环容量衰减仅 2 1.8%。另外 ,还用X射线衍射检测了贮氢合金的微观结构     

含锆镁基储氢合金的合成及其电化学性能

用固相扩散法合成了Mg2-xZrxNi (x=0, 0.2, 0.3, 0.4, 0.5, 0.6)系列合金. XRD结构分析表明 主相仍为Mg2Ni; Zr替代Mg使合金的微晶结构发生了改变, 趋于非晶化; 添加Zr的合金的容量比由扩散法合成的合金的容量有所提高; 合金中添加Zr, 提高了电极的放电容量, 增大了放电平台; 特别是Zr 对六方晶系Mg2Ni合金结构中Mg的部分取代大幅度提高了电极的循环寿命, 未经任何处理的 Mg1.4Zr0.6Ni合金电极经25个循环后, 放电容量仅衰减4.11%, 表明添加Zr对提高合金的循环寿命具有重要的作用.     

Effect of photocatalyst on performance of LaNi5 hydrogen storage alloy electrodes

Photocatalyst hydrogen storage alloys（PHSA） with different photocatalyst contents were synthesized by mechanical blend method. The effects of the photocatalyst on the electrochemical performance of the PHSA were studied. The resutts indicate that the PHSA electrodes show better activation performance when UV irradiation is present. The high rate discharge performance as well as cycle performance is improved compared with that of the AB5 alloys, The PHSA shows the best performance when the photocatalyst content is 20%.     

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi3.55Mno.35Co0.20Al0.20Cuo.75Fe0.10 hydrogen storage alloys were investigated.X-ray diffraction (XRD) analysis indicated that annealing treatment remarkably reduced the lattice strain and defects,and increased the unit-cell volume.The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation,which gradually disappeared with increasing annealing temperature,and the microstructure changed to an equiaxed structure after annealing the alloy at 1233 K.The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one.The capacity retention at the 100th cycle increased from 90.0％(as-cast) to 94.7％ (1273 K).The annealing treatment also improved the discharge capacity.However,the high rate dischargeability (HRD)value of the annealed alloy slightly dropped,which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.     

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi_3.55Mn_0.35Co_0.20Al_0.20Cu_0.75Fe_0.10 hydrogen storage alloys were investigated. X-ray diffraction (XRD) analysis indicated that annealing treatment remarkably reduced the lattice strain and defects, and increased the unit-cell volume. The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation, which gradually disappeared with increasing annealing temperature, and the microstructure changed to an equiaxed structure after annealing the alloy at 1233 K. The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one. The capacity retention at the 100th cycle increased from 90.0% (as-cast) to 94.7% (1273 K). The annealing treatment also improved the discharge capacity. However, the high rate dischargeability (HRD) value of the annealed alloy slightly dropped, which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.     

Study on hydrogen diffusion behavior in MlNi_(3.75) Co_(0.65) Mn_(0.4) Al_(0.2) alloy electrode by chronoamperometry

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Co对MlNi4.3-xCoxAl0.7贮氢电极动力学性能的影响

详细研究了Ｃｏ 对ＭｌＮｉ４ ．３ － ｘＣｏｘＡｌ０ ．７（ ｘ ＝ ０ , ０ ．３ , ０ ．５ ,０ ．７ ,０ ．９ ,１ ．１ ,１ ．３） 贮氢电极的动力学特性的影响; 研究的动力学参数包括高倍率放电特性ＨＲＤ、交换电流密度Ｊ０ 、极限电流密度ＪＬ、对称因子β以及氢在α相中的扩散系数Ｄα。实验结果表明： 随着ＭｌＮｉ４ ．３ － ｘＣｏｘＡｌ０ ．７ 贮氢电极中Ｃｏ 含量的增大, 合金的高倍率放电能力迅速减小, 交换电流密度Ｊ０ , 极限电流密度ＪＬ, 对称因子β以及氢在α相中扩散系数Ｄα显著降低     

Nd替代La对La-Mg-Ni系A2B7型贮氢电极合金性能的影响

用冷坩锅磁悬浮熔炼方法制备了La0.7-xNdxMg0.3(NiCoAl)3.5(x=0,0.1,0.3,0.5,0.7)贮氢电极合金,采用X射线衍射Rietveld法、三电极体系及扫描电镜研究合金的相结构和电化学性能以及电极的表面状态。Rietveld法分析表明:合金为多相结构,主相均为Ce2Ni7型六方相,还包括CaCu5型六方相、PuNi3型菱方相、MgCu2型立方相及CrB型正交相;且随着Nd含量x的增加,主相含量增加,相应CaCu5型和MgCu2型相含量降低,PuNi3型相含量则在一定范围内波动;且各组成相单胞体积均呈线性降低趋势。p—c—t曲线显示,合金放氢平台区域变窄,平台压力升高,平台先稍有倾斜后逐渐平坦。电化学性能测试显示,最大放电容量基本呈线性递减;活化性能优异;高倍率放电性能先提高后稍有降低;循环稳定性得到改善。     

温度对La-Mg-Ni-Co-Mn贮氢电极合金电化学性能的影响

系统研究了温度对La07Mg03Ni2875Co0.525Mn0.1贮氢合金电化学性能尤其是电化学动力学性能的影响.结果表明:La07Mg03Ni2 875Co0525Mn0,合金由(La,Mg)Ni3相和LaNi5相构成.合金的最大放电容量随着温度升高从-20℃时的277.5 mAh/g增加到30℃时的406.2 mAh/g.随着温度升高,合金放电平台电位逐渐变负,放电过电位逐渐减小,合金电极的极化减弱.高倍率性能、交换电流密度、氢的扩散系数研究表明合金的电化学动力学性能随着温度升高不断提高.该合金的氢扩散活化能为17.6 KJ/mol.     

Synergistic effect between Laves phase and Zr Ni phases in Zr(MnVNi)_2 hydrogen storage alloys

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TiV_(2.1)Ni_x(x=0.2~0.6)贮氢合金的相结构及电化学性能

系统研究了TiV2.1Nix(x=0.2,0.3,0.4,0.5,0.6)贮氢合金的相结构及电化学性能。XRD及SEM分析表明:合金均由体心立方(bcc)结构的V基固溶体主相和TiNi基第二相组成;随着Ni含量x的增加,合金中V基固溶体主相的相含量和晶胞参数逐渐减小,TiNi基第二相含量逐渐增多,且当x≥0.4时,TiNi基第二相组织沿主相晶界形成明显的三维网络状结构。电化学测试表明:随着x的增加,合金的高倍率放电性能及循环稳定性均得到显著改善;但当x从0.4增加到0.6时,合金的活化性能变差,最大放电容量降低。在研究的合金中,TiV2.1Ni0.4表现出较好的综合性能。     

Effect of commercial AB5 alloy addition on the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys

A commercial AB5 hydrogen storage alloy was used as an additive to improve the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys.The effect of AB5 alloy addition on the phase structure,charge/discharge characteristics,and electrochemical kinetics of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy was investigated.The maximum discharge capacity of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 electrode reaches 406 mAh/g.The anodic polarization,cyclic voltammetry,and potential step discharge experiments show that the electrochemical kinetics of the electrode with additives was promoted,with the LaNi5 phase of AB5 alloy acting as electro-catalytic sites in the electrode alloy.The high-rate dischargeability of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 alloy electrode at 1100 mA/g reaches 60.9%,which is 9.4% higher than that of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy electrode.The cycling stability of the electrode with 4 wt.% AB5 alloy has also been improved.     

La0.8-χREχMg0.2Ni3.2CO0.6储氢合金的结构及电化学性能

通过感应容炼制备了La0.8-xREMg0.2Ni3.2Co0.6(RE=Sm,Dy,0≤x≤0.3)合金.采用X射线衍射分析了该合金的晶体结构,并研究了其电化学性能.结果表明该合金是由LaNi5主相和LaNi3第二相构成;随着Sm(Dy)取代La量的增加,合金主相单胞体积线性收缩,合金储氢量和放电容量减小,当Sm(Dy)取代量分别为0.1、0.2、0.3时,合金容量由380 mA·h/g分别减小到370(362)、355(334)、329(295)mA·h/g,但高倍率放电能力和循环稳定性得到改善,100次循环后的容量损失率由20%分别降低到18%(17%)、16%(14%)、13%(11%).     

Structure and electrochemical properties of low-cobalt La1- xLixNi3.2Co0.3Al0.3(0≤x≤0.2) hydrogen storage electrode alloys

The structure and electrochemical properties of a new low cobalt hydrogen storage electrode alloys La1-xLixNi3.2Co0.3Al0.3(0≤ x ≤0.2) were investigated with a different additions of Li in replacement of La. With the increase of Li contents the maximum discharge capacity increases from 240 mAh·g -1 ( x =0) to 328.4 mAh·g -1(x=0.1) and the cycle stability is improved correspondingly. The capacity decay can remaiN28.6% ( x =0.2) after 230 charge/discharge cycles. The high rate discharge(HRD) ability of the alloys( x≤0.1) is improved and the best HRD is 34.1%( x =0.1) under the discharge current density 1200 mA·g -1 . It is found that the prepared alloys are basically composed of LaNi5 as matrix phase and LaNi3 as second phase( x ≤0.1). But the abundance of LaNi3 phase dramatically decreases with increasing x . When x =0.2, a new phase Al(NiCo)3 is formed.     

Effects of rapid quenching on microstructures and electrochemical properties of La0.7Mg0.3Ni2.55Co0.45Bx（x=O-0.2） hydrogen storage alloy

In order to improve the electrochemical performances of La-Mg-Ni based electrode alloys with PuNi3-type structure, a trace of boron was added in La0.7Mg0.3Ni2.55Co0.45 alloy. The La0.7Mg0.3Ni2.55Co0.45Bx（a=0, 0.05, 0.1, 0.15 and 0.2） alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were investigated. The effects of rapid quenching on the microstructures and electrochemical performances of the above alloys were investigated. The results show that the as-cast and quenched alloys are composed of （La, Mg）Ni3 phase, LaNi5 phase and LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloys containing boron, and the Ni2B phase in the B-contained alloys nearly disappears after rapid quenching. Rapid quenching increases the amount of the LaNi2 phase in the B-free alloy, but it decreases the amount of the LaNi2 phase in the boron-containing alloys. The effects of rapid quenching on the capacities of the boron-containing and boron-free alloys are different. The capacity of the B-free alloy monotonously decreases with increasing quenching rate, whereas the capacities of the B-contained alloys have a maximum value with the change of the quenching rate. The rapid quenching can improve the stability of La-Mg-Ni based electrode alloy but lowers the discharge plateau voltage and decreases the plateau length. The effect of rapid quenching on the activation capabilities of the alloys was complicated.