The performances of proto-type Ni/MH secondary batteries using Zr-based hydrogen storage alloys and filamentary type Ni

Abstract

For the purpose of developing a Zr-based Laves phase alloy with higher capacity and better performance for electrochemical application, extensive work has been carried out. After careful alloy design of ZrMn₂-based hydrogen storage alloys through varying their stoichiometry by means of substituting or adding alloying elements, the Zr_0.9Ti_0.1(Mn_0.7V_0.5Ni_1.4)_0.92 with high capacity (392 mAh/g at the 0.25C) and improved performance (comparable to that of commercialized AB₅ type alloy) was developed. Another endeavor was made to improve the poor activation property and the low rate capability of the developed Zr-based Laves phase alloy for commercialization. The combination method of hot-immersion and slow-charging was introduced. It was found that electrode activation was greatly improved after hot immersion at 80°C for 12h followed by charging at 0.05C. The effects of this method are discussed in comparison with other activation methods. The combination method was successfully applied to the formation process of 80 Ah Ni/MH cells. A series of systematic investigations has been rendered to analyze the inner cell pressure characteristics of a sealed type Ni-MH battery. It was found that the increase of inner cell pressure in the sealed type Ni/MH battery of the above-mentioned Zr−Ti−Mn−V−Ni alloy was mainly due to the accumulation of oxygen gas during charge/discharge cycling. The fact identified that the surface catalytic activity was affected more dominantly by the oxygen recombination reaction than the reaction surface area was also identified. In order to improve the surface catalytic activity of a Zr−Ti−Mn−V−Ni alloy, which is closely related to the inner pressure behavior in a sealed cell, the electrode was fabricated by mixing the alloy with Cu powder and a filamentary type of Ni and replacing 75% of the carbon black with them; thus, the inner cell pressure rarely increases with cycles due to the active gas recombination reaction. Measurements of the surface area of the electrode and the surface catalytic activity showed that the surface catalytic activity for the oxygen recombination reaction was greatly improved by the addition of Cu powder and the filamentary type of Ni. Finally, we have collaborated with Hyundai Motors Company on fabrication of the 80Ah cells for Electric Vehicles and evaluated the cell performance.