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Fe 对 LaCeNi 合金储氢性能的影响。

Influence of Fe on the Hydrogen Storage Properties of LaCeNi Alloys.

机构信息

Institute of Physics of Materials, Czech Academy of Sciences, Zizkova 513/22, 61600 Brno, Czech Republic.

ENET Centre─Research Centre of Energy Units for Utilization of Non Traditional Energy Sources, VSB-TUO, 17. Listopadu 2172/15, 708 00 Ostrava-Poruba, Czech Republic.

出版信息

Langmuir. 2023 May 2;39(17):6061-6068. doi: 10.1021/acs.langmuir.3c00093. Epub 2023 Apr 20.

Abstract

LaNi intermetallic compounds with a hexagonal CaCu type structure can react reversibly with hydrogen. The element substitutions in LaNi can significantly change the hydrogenation properties, allowing to tune them to a large extent. It could be very advantageous to partially replace Ni or La with other elements to reduce the cost of this alloy as well as the equilibrium pressure of absorption and desorption. The hydrogen storage properties of ball-milled AB alloys containing the elements La, Ce (A-rare elements) and Ni, Fe (B-transition metals) were studied in this paper. Although the substitution of Ni (atomic radius 1.49 Å) with Fe atom (atomic radius 1.56 Å) increased the unit cell volume from 86.4149 to 87.947 5 Å of the LaNi phase, its hydrogen storage capacity was still close to the value 1.4 wt %. The enthalpy (Δ) of hydride formation for hydrogen absorption and desorption of the experimental alloys was in the range of 29-32.6 kJ/mol. A very favorable effect of Fe on the sorption properties was found in the significant reduction of the equilibrium pressure of absorption and desorption. These studied experimental Fe-containing alloys were able to store hydrogen at 300 K and with pressure under 0.1 MPa. The fastest sorption kinetics of hydrogen was found in alloys with FeNi phase particles located on the surface of the powder. However, if the FeNi phase was segregated at the grain boundaries, it acted as a barrier limiting the growth of the hydride phase. This led to a decrease of the hydride sorption kinetics.

摘要

LaNi 型六方钙铜结构的金属间化合物可以与氢发生可逆反应。LaNi 中的元素取代可以显著改变其加氢性能,从而在很大程度上对其进行调节。通过用其他元素部分替代 Ni 或 La,来降低这种合金的成本以及吸氢和解吸的平衡压力,这将是非常有利的。本文研究了含有 La、Ce(A-稀土元素)和 Ni、Fe(B-过渡金属)元素的 AB 合金球磨后的储氢性能。尽管用原子半径为 1.56 Å 的 Fe 原子替代 Ni(原子半径为 1.49 Å)会使 LaNi 相的单位晶胞体积从 86.4149 Å 增加到 87.9475 Å,但它的储氢能力仍接近 1.4wt%。实验合金的氢吸收和解吸的焓(Δ)在 29-32.6 kJ/mol 之间。在显著降低吸氢和解吸的平衡压力方面,Fe 对吸氢性能有非常有利的影响。这些研究的含 Fe 实验合金能够在 300 K 和 0.1 MPa 以下的压力下储存氢气。在位于粉末表面的 FeNi 相颗粒的合金中发现了最快的吸氢动力学。然而,如果 FeNi 相在晶界处偏析,则会作为限制氢化物相生长的障碍。这导致了氢化物吸氢动力学的降低。

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