化学计量比对AB5型贮氢合金相结构及电化学性能的影响

对低钴稀土系贮氢合金Ml(Ni0.78Co0.08Al0.06Mn0.08)x(4.8≤x≤5.4)的相结构及电化学性能进行了研究.结果表明在4.8≤x≤5.2的合金中除CaCu5型结构的主相之外,还出现LaNi3第二相,而且合金中第二相(LaNi3)的析出量随着x值的增大而减少,化学计量比x=5.4的合金则有富镍相析出,B侧合金化使低钴贮氢合金形成单相AB5型合金的化学计量比由x=5.0增大至5.2～5.4之间.四种不同化学计量比合金的活化性能都较好,合金的最大放电容量随化学计量比x的增大而增加,过化学计量比(x=5.4)合金具有最大的放电容量,最优的放电电压特性及最佳的循环稳定性,且其高倍率放电性能也较好.     

替代元素对低钴贮氢合金性能的影响

在AB5型贮氢合金MlNi3.55Co0.75Al0.3Mn0.4钴含量基础上,B侧采用Cu、Fe、Zn、Cr元素替代Co,A侧加入Dy来制备低钴贮氢合金.并对合金的放电容量、循环稳定性以及微观结构进行了研究分析.研究表明,通过调整合金成分可以使贮氢合金具有较好的组织均匀性和综合电化学性能.     

Cu掺杂对贮氢合金MI(NiCoMnAlCu)5.0电化学性能的影响

采用真空感应熔炼方法,制备了一系列Cu掺杂的MI(NiCoMnAlCu)5.0即AB50型贮氢合金.通过电化学及X射线衍射等手段,系统地研究和分析了Cu掺杂对AB50型贮氢合金的电化学性能(最大放电比容量、高倍率性能和循环稳定性能)及其微结构和动力学特征的影响.     

Cu掺杂对贮氢合金MI（NiCoMnAICu）5．0电化学性能的影响

采用真空感应熔炼方法，制备了一系列Cu掺杂的MI（NiCoMnAtCu）5.0即AB5.0型贮氢合金。通过电化学及X射线衍射等手段，系统地研究和分析了Cu掺杂对AB5.0型贮氢合金的电化学性能（最大放电比容量、高倍率性能和循环稳定性能）及其微结构和动力学特征的影响。     

稀土基AB5型复合贮氢合金的研究进展

制备复合合金是改善贮氢合金性能的一条有效途径。本文对国内外各种多元以及多相稀土复合贮氢材料的研究现状进行了综合评述，主要涉及了AB5-AB2型复合贮氢合金和镁基-AB5型纳米复合贮氢合金的进展。阐述了各种复合材料的组成，微观结构以及电化学性能等，并展望了今后复合贮氢材料的研究方向为应用基础性的研究，如复合作用机制、对热力学性能的影响等方面的研究。     

Ni/MH电池用AB_5型贮氢合金电极研究进展

综述AB_5型贮氢合金电极的研究现状, 总结了目前改善AB_5型稀土系贮氢合金综合性能的方法.详细介绍了合金成分优化,控制合金组织结构,形成第二相和表面处理等方面的研究进展.通过这些途径,可以对AB_5型贮氢合金进行深入研究,从而进一步提高合金的性能.     

镍氢电池用无钻AB5型贮氢合金的研究进展

自从1990年前后小型MH-Ni电池商业化以来,镍氢电池的生产与销售都有了快速的增长。AB5型稀土镍系贮氢合金由于具有优良的性能价格比,是目前镍氢电池（MH—Ni）电池生产中实际应用最为广泛的负极材料。AB5型贮氢合金的放电容量已经达到一定的高度,目前,贮氢合金所需原材料金属Co及稀土元素钕和镨价格涨幅很快,因此拓宽MH-Ni电池的应用领域,提高其在电池领域的竞争力比较现实的途径是降低贮氢合金的生产成本。     

制备工艺对无钴AB5型贮氢合金的相结构和电化学性能的影响

用真空熔炼、快淬工艺以及球磨工艺制备稀土基无钴AB5型La（NiMnAlFe）5贮氢合金，用XRD测试了合金的相结构，并测试了不同制备工艺下合金的电化学性能。研究了制备工艺对无钴合金的相结构和电化学性能的影响。结果表明，由真空熔炼和快淬工艺制备的合金为CaCu5型单相结构，球磨合金由CaCu5型相和游离Ni相组成，并出现了非晶化趋势。快淬和球磨均使合金的放电容量降低，循环稳定性提高，但球磨工艺的影响更为显著，主要原因是球磨后合金中出现非晶化趋势。     

铝在新型稀土镁基AB3型贮氢电极合金中的作用研究

借助于自制的开口式H型玻璃三电极测试体系，并在大量的前期实验工作基础上，研究了新型稀土镁基AB3型贮氢电极合金的性能以及添加Al的作用。发现用适量Al替代Ni可降低稀土镁基AB3型合金La0.7Mg0.3（Ni0.85Co0．15）3.5的氢化反应焓变和气态放氢平台压力，使合金氢化物变得更稳定；同时，使合金电化学循环100周期的容量保持率从63．8％提高到90．6％，有效解决了合金放电容量迅速衰减的难题；但Al的添加也降低了合金的最大放电容量、倍率放电性能和活化性能。     

低钴稀土系贮氢合金的研究

通过在稀土系贮氢合金中添加不同含量的Fe或Cu元素,部分替代合金中Co的方法,研究低钴贮氢合金电化学性能上的差异.结果表明:由于合金组成和化学计量比的不同,同样是添加了Fe或Cu的合金在电化学性能上表现不同,但总体说,含Cu低钴贮氢合金容量和倍率放电性能较好,含Fe低钴贮氢合金有较好的循环稳定性,过化学计量比的合金循环稳定性要好于欠化学计量比的合金.     

Effect of praseodymium substitution for lanthanum on structure and properties of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（X=0.00-0.20） hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La, Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase, (La,Mg)Ni2 phase and (La, Mg)(Ni,Al)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Elec-trochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=0.00) to 335 mAh/g (x=0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.     

Microstructure and electrochemical characteristics of La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x（V0.81Fe0.19）x hydrogen storage alloys

Microstructure and electrochemical characteristics of La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x(V0.81Fe0.19)x hydrogen storage alloys were investigated. XRD indicated that La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x(V0.81Fe0.19)x alloys consisted of a single phase with CaCu5-type structure, and the lattice parameter a and cell volume V increased with increasing x value. The maximum discharge capacity first increased from 319.0 (x=0) to 324.0 mAh/g (x=0.05), and then decreased to 307.0 mAh/g (x=0.20). The high-rate dischargeability at the discharge current density of 1200 mA/g first increased from 52.1% (x=0) to 59.1% (x=0.15), and then decreased to 55.4% (x=0.20). The hydrogen diffusion in the bulky alloy was responsible for the high-rate dischargeability. Cycling stability first increased with increasing x from 0 to 0.10 and then decreased when x increased to 0.20, which was resulted from the synthesized effect of the improvement of the pulverization resistance and the decrease of corrosion resistance.     

RE-Mg-Ni系储氢合金高倍率放电性能研究现状

RE-Mg-Ni系储氢合金具有超晶格结构,其主相晶格单元是由一定比率的AB5单元和AB2单元沿c轴交替层叠排列而成。该类型合金自问世以来便以其高容量、易活化的优势受到人们的广泛关注,然而其循环稳定性及高倍率放电性能不尽人意。人们通过大量研究有效提高了其循环稳定性,使其基本满足了商业化要求。但是要将基于该负极材料的镍氢电池应用在混合动力汽车上,仍需改进其高倍率放电性能。系统分析了元素替代、多元合金化、制备工艺、化合物复合、表面处理等手段对RE-Mg-Ni系储氢合金晶体结构及高倍率放电性能的影响。其中元素替代是一种重要且有效的手段,文中分析了不同稀土元素及B侧元素的作用机制,结果表明,B侧组分采用Ni,Co,Mn,Al的储氢合金具有较好的性能。多元合金化是一种复杂的过程,不同元素间可能存在一定的协同作用,研究其作用机制也是下一步的工作重点。通过优化实验方案,综合使用多种改性手段,可以得到高倍率放电性能良好的RE-Mg-Ni系储氢合金,使其基本满足电动工具用镍氢电池的要求,并可望在以后的研究中进一步提高其高倍率放电性能,使其满足混合动力汽车用镍氢电池的要求,实现良好的经济和社会效益。     

Phase Structure and Electrochemical Characteristics of Ml（Ni3.55Co0.75Mn0.40Al0.30）5x （x=0.88, 0.92, 0.96, 1.00） Hydrogen Storage Alloys

The phase structure and electrochemical characteristics of Ml （（Ni3.55Co0.75Mn0.40Al0.30）sx （ x = 0.88, 0.92, 0.96, 1.00） hydrogen storage alloys were studied. The effect of the stoichiometric ratio on the phase structure and electrochemical characteristics was analyzed. The results of XRD reveal that all the alloys consist mainly of LaNi5 phase with the hexagonal CaCu5 structure. But a few of the diffraction peaks of La2Ni7 phase on XRD pattern are observed when x ≤ 0.92, and with decreasing x, the intensity of La2Ni7 diffraction peaks increases and the values of lattice parameters a and cell volume increase, c and c/a of LaNi5 phase decrease gradually. When x≥0.96, La2Ni7 phase disappears and the alloys become single CaCu5-type. The electrochemical tests show that the maximum discharge capacity, high rate dischargeability and low temperature dischargeability are improved to different degrees by adjusting the stoichiometric ratio.     

Composition optimization and electrochemical characteristics of Co-free Fe-containing AB5-type hydrogen storage alloys through uniform design

In order to reduce the cost of AB5-type hydrogen storage alloys, effects of substitution of Ce for La (A side) and Fe, Mn, Al for Ni (B side) on structural and electrochemical properties of (LaCe)1(NiFeMnAl)5 alloys were studied systematically. To make component uniform and operation easy, uniform design (UD) method was introduced into the study of composition optimization of Co-free Fe-containing AB5-type alloys for the first time. X-ray diffraction (XRD) results showed that the designed alloys were of single CaCu5-type structure phase. The replacement of Fe had a severe effect on electrochemical capacity, and the substitution of Fe and Al had a synergetic action among the unit cell volume, cycling stability and high rate discharge property. Interestingly, it was found that the hydrogen storage alloys with exces-sively high plateau pressure showed a tilted line in Nyquist plot instead of the semicircle, and the current decayed rapidly to near zero at the beginning of the step in constant potential step (CPS), indicating that electrochemical impedance spectra (EIS) and CPS cannot accurately measure the electrochemical kinetics process of the hydrogen storage alloys with excessively high plateau pressure.     

Effect of surface treatment on the structure and high-rate dischargeability properties of AB5-type hydrogen storage alloy

Surface-treated MmNi3.55Co0.75Mn0.4Al0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCI aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray dif-fraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties before and after surface treatment were compared, and the alloy treated in 0.025 mol/L HCI solution showed the optimal high-rate dischargeability.     

Effect of surface treatment on the structure and high-rate dischargeability properties of ABs-type hydrogen storage alloy

Surface-treated MmNi_3.55Co_0.75Mn_0.4Al_0.3 alloy as negative electrode material of nickel-metal hydride battery was employed to improve the high-rate dischargeability. Surface treatment was realized by dipping and stirring the alloy into a HCl aqueous solution with various concentrations at room temperature. The microstructure of the alloy before and after surface treatment was analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties before and after surface treatment were comparedand the alloy treated in 0.025 mol/L HCl solution showed the optimal high-rate dischargeability.     

Effect of rapid solidification treatment on structure and electrochemical performance of low-Co AB5-type hydrogen storage alloy

The effect of rapid solidification on structure and electrochemical performance of the LaNi4.5Co0.25Al0.25 hydrogen storage alloy was investigated by X-ray powder diffraction and a simulated battery test, including maximum capacity, cycling stability, self-discharge, and high-rate discharge ability （HRD）. All the melt-spun alloys were single-phase with the CaCu5-type structure （space groupP6/mmm）. In comparison to the as-cast alloy, the rapidly quenched alloys manifested an improved homogeneity of com-position and expanded lattice parameters. The electrochemical measurements showed that the activation property, cycling stability and self-discharge of the alloy electrodes were also improved for the rapid solidified alloys. The HRDof the as-cast alloy was better than those of all the rapidly solidified alloys. As the quenching rate increased, the HRD and exchange current density first decreased and then increased.     

Relations between Quenching Rate and Electrochemical Characteristics of Mm (NiCoMnA1) 5Bx (x=0～0.2) Electrode Alloys

Low-Co AB5-type Mm(NiCoMnA1)5Bx (x = 0, 0.1, 0.2 ) electrode alloys were prepared by casting and rapid quenching.The effects of the rapid quenching on the lattice constants, microstructures and electrochemical characteristics of the alloys were investigated in detail.The obtained results show that the rapid quenching made lattice constants and cell volume increased.In a range of the quenching rate, rapid quenching can increase the discharge capacities of the alloys.However, the discharge capacity of the as-quenched alloy is lower than that of the as-cast alloy when quenching rate is more than a critical value.The cycle lives of the alloys increase monotonously with the increase of the quenching rate.     

Effect of the partial substitution of samarium for lanthanum on the structure and electrochemical properties of La_(15)Fe_(77)B_8-type hydrogen storage alloys

La15Fe77B8 hydrogen storage alloys were prepared using a vacuum induction-quenching furnace. The results of X-ray diffraction(XRD) and scanning electron microscopy(SEM) suggested that La15–xSmxFe2Ni76Mn5B2(x=0, 2, 4, 6) alloys had multiphase structure including the main LaNi5 phase, La3Ni13B2 phase and(Fe, Ni) phase. With the increasing substitution of Sm for La, the main phase structure of alloys did not change, while the unit cell volumes decreased, the cycle stability was improved and the maximum discharge capacity decreased, but the low temperature maximum discharge capacity of the same substitution alloy was gradually approaching the maximum discharge capacity at room temperature, which showed that La15Fe77B8 hydrogen storage alloys of the partial substitution of Sm for La had better low-temperature dischargeability(LTD). For the same substitution alloys, self-discharge characteristics and cycle stability at low temperature were better than that at room temperature. Furthermore, the high-rate dischargeability(HRD) and the exchange current density I0 first increased and then decreased with the increasing of Sm content, whereas the hydrogen diffusion coefficient D in alloy bulk decreased gradually, which indicated that appropriate substitution of Sm for La improved the electrochemical kinetics properties of the alloys. The HRD was mainly dominated by the charge-transfer rate on the alloy surface.