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Fe-Substitution for Ni in Misch Metal-Based Superlattice Hydrogen Absorbing Alloys—Part 1. Structural, Hydrogen Storage, and Electrochemical Properties

机译:Misch金属基超晶格吸氢合金中Ni的铁取代-第1部分。结构,储氢和电化学性质

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摘要

The effects of Fe partially replacing Ni in a misch metal-based superlattice hydrogen absorbing alloy (HAA) were studied. Addition of Fe increases the lattice constants and abundance of the main Ce 2 Ni 7 phase, decreases the NdNi 3 phase abundance, and increases the CaCu 5 phase when the Fe content is above 2.3 at%. For the gaseous phase hydrogen storage (H-storage), Fe incorporation does not change the storage capacity or equilibrium pressure, but it does decrease the change in both entropy and enthalpy. With regard to electrochemistry, >2.3 at% Fe decreases both the full and high-rate discharge capacities due to the deterioration in both bulk transport (caused by decreased secondary phase abundance and consequent lower synergetic effect) and surface electrochemical reaction (caused by the lower volume of the surface metallic Ni inclusions). In a low-temperature environment (?40 °C), although Fe increases the reactive surface area, it also severely hinders the ability of the surface catalytic, leading to a net increase in surface charge-transfer resistance. Even though Fe increases the abundance of the beneficial Ce 2 Ni 7 phase with a trade-off for the relatively unfavorable NdNi 3 phase, it also deteriorates the electrochemical performance due to a less active surface. Therefore, further surface treatment methods that are able to increase the surface catalytic ability in Fe-containing superlattice alloys and potentially reveal the positive contributions that Fe provides structurally are worth investigating in the future.
机译:研究了在混合金属基超晶格吸氢合金(HAA)中Fe部分替代Ni的影响。当Fe含量高于2.3at%时,添加Fe增加了主Ce 2 Ni 7相的晶格常数和丰度,降低了NdNi 3相的丰度,并增加了CaCu 5相。对于气相氢存储(H存储),Fe的掺入不会改变存储容量或平衡压力,但会降低熵和焓的变化。就电化学而言,> 2.3 at%的铁会降低整体和高倍率放电容量,这是由于整体传输(由于降低的第二相丰度和随之而来的较低的协同作用)和表面电化学反应(由于较低的介电常数)引起的表面金属Ni夹杂物的体积)。在低温环境中(约40°C),尽管Fe增加了反应表面积,但也严重阻碍了表面催化能力,导致表面电荷转移电阻的净增加。即使Fe以相对不利的NdNi 3相为代价而增加了有益的Ce 2 Ni 7相的丰度,但由于活性较低的表面,它也使电化学性能劣化。因此,将来能够研究能够提高含铁超晶格合金的表面催化能力并潜在揭示铁在结构上提供的积极作用的其他表面处理方法。

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