添加Si对A2B7型电极合金结构及电化学贮氢性能的影响

摘要

In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six (x=0-0.2) electrode alloys were prepared by casting and annealing. The effects of adding Si on the structure and electrochemical hydrogen storage characteristics of the alloys were investigated systematically. The results indicate that the as-cast and annealed alloys hold multiple structures, involving two major phases of (La, Mg)2Ni7 with a Ce2Ni7-type hexagonal structure and LaNi5 with a CaCu5-type hexagonal structure as well as one residual phase LaNi3. The addition of Si results in a decrease in (La, Mg)2Ni7 phase and an increase in LaNi5 phase without changing the phase structure of the alloys. What is more, it brings on an obvious effect on electrochemical hydrogen storage characteristics of the alloys. The discharge capacities of the as-cast and annealed alloys decline with the increase of Si content, but their cycle stabilities clearly grow under the same condition. Furthermore, the measurements of the high rate discharge ability, the limiting current density, hydrogen diffusion coefficient as well as electrochemical impedance spectra all indicate that the electrochemical kinetic properties of the electrode alloys first increase and then decrease with the rising of Si content.%为改善La-Mg-Ni 系 A2B7型合金的电化学贮氢性能，在合金中添加一定量的Si元素，通过真空熔炼及退火处理的方法制备La0.8Mg0.2Ni3.3Co0.2Six (x=0-0.2)电极合金。研究Si元素的添加对合金结构及电化学贮氢性能的影响。结果表明，铸态及退火态合金均为多相结构，分别为Ce2Ni7型的(La, Mg)2Ni7相和CaCu5型的LaNi5相以及少量的残余相LaNi3。Si元素的添加没有改变合金的主相，但使得合金中的(La, Mg)2Ni7相减少而LaNi5相增加。添加Si显著地影响了合金的电化学性能。随着Si含量的增加，铸态及退火态合金的放电容量逐步降低，但循环稳定性却随着Si含量的增加而增强。此外，合金电极的高倍率放电性能、极限电流密度、氢扩散系数以及电化学交流阻抗谱的测试均表明合金的电化学动力学性能随着Si含量的增加先增加而后减小。