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Abstract:Herein, we present a comparison of the electrochemical hydrogen-storage characteristics of two state-of-art Laves phase-based metal hydride alloys (Zr 21.5 (V and Cr) in the first composition results in an average electron density below the C14/C15 threshold ( e/a ∼ 6.9) and produces a C14-predominated structure, while the average electron density of the second composition is above the C14/C15 threshold and results in a C15-predominated structure. From a combination of variations in composition, main phase structure, and degree of homogeneity, the C14-predominated alloy exhibits higher storage capacities (in both the gaseous phase and electrochemical environment), a slower activation, inferior high-rate discharge, and low-temperature performances, and a better cycle stability compared to the C15-predominated alloy. The superiority in high-rate dischargeability in the C15-predominated alloy is mainly due to its larger reactive surface area. Annealing of the C15-predominated alloy eliminates the ZrNi secondary phase completely and changes the composition of the La-containing secondary phase. While the former change sacrifices the synergetic effects, and degrades the hydrogen storage performance, the latter may contribute to the unchanged surface catalytic ability, even with a reduction in total volume of metallic nickel clusters embedded in the activated surface oxide layer. In general, the C14-predominated alloy is more suitable for high-capacity and long cycle life applications, and the C15-predominated alloy can be used in areas requiring easy activation, and better high-rate and low-temperature performances.

Abstract:The performance of cylindrical cells made from negative electrode active materials of two selected AB 2 metal hydride chemistries with different dominating Laves phases (C14 vs. C15) were compared. Cells made from Alloy C15 showed a higher high-rate performance and peak power with a corresponding sacrifice in capacity, low-temperature performance, charge retention, and cycle life when compared with the C14 counterpart (Alloy C14). Annealing of the Alloy C15 eliminated the ZrNi secondary phase and further improved the high-rate and peak power performance. This treatment on Alloy C15 showed the best low-temperature performance, but also contributed to a less-desirable high-temperature voltage stand and an inferior cycle stability. While the main failure mode for Alloy C14 in the sealed cell is the formation of a thick oxide layer that prevents gas recombination during overcharge and consequent venting of the cell, the failure mode for Alloy C15 is dominated by continuous pulverization related to the volumetric changes during hydride formation and hysteresis in the pressure-composition-temperature isotherm. The leached-out Mn from Alloy C15 formed a high density of oxide deposits in the separator, leading to a deterioration in charge retention performance. Large amounts of Zr were found in the positive electrode of the cycled cell containing Alloy C15, but did not appear to harm cell performance. Suggestions for further composition and process optimization for Alloy C15 are also provided.