METALS AND MATERIALS International, Vol. 7, No. 2 (2001), pp. 181~186 The Performances of Proto-Type Ni/MH Secondary Batteries Using Zr-Based Hydrogen Storage Alloys and Filamentary Type Ni Sang-Min Lee, Ho Lee, Jin-Ho Kim, Paul S. Lee, and Jai-Young Lee Department of Material Science and Engineering Korea Advanced Institute of Science and Technology 373-1 Kusong-dong, Yusong-ku, Taejon 305-701, Korea 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 ZrMn 2 - based hydrogen storage alloys through varying their stoichiometry by means of substituting or adding alloying elements, the Zr 0.9 Ti 0.1 (Mn 0.7 V 0.5 Ni 1.4 ) 0.92 with high capacity (392 mAh/g at the 0.25C) and improved performance (comparable to that of commercialized AB 5 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 o C for 12 h 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 inves- tigations 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. Keywords : metal hydride, Zr-based laves phase alloy, Ni-MH battery, filamentary Ni, surface catalytic activity 1. INTRODUCTION Nickel-metal hydride (Ni-MH) batteries using hydrogen storage alloys as negative electrodes have been developed and commercialized to meet the strong market demand for a power source with high energy density, high rate capability, long cycle life, and good environmental compatibility. In order to further improve the energy density of Ni-MH batter- ies, Zr-based Laves alloys should replace the commercial MmNi 5 -type alloys, which have reached their energy density limitations [1-3]. Therefore, much research has focused on developing such based alloys with a high capacity for electro- chemical applications. There have been many endeavors to develop these alloys with high discharge capacity; however, in order to apply this alloy in practical Ni-MH battery sys- tems, the performance (i.e. rate-capability, activation property and inner cell pressure) should be enhanced to the level of commercial alloys. In this paper, we introduce our recent work on the improvement of the cell performance. It has been reported that rate-capability is mainly controlled by surface reaction kinetics, which depends on the metallic Ni or some Ni-rich phase on the alloy surface [4,5]. On the other hand, it was recently reported that some hyper-stoichio- metric Zr-based Laves phase alloys showed excellent hydrid- ing and electrochemical characteristics compared with those of the stoichiometric alloys [6]. In this work, extensive stud- ies have been carried out to develop a Zr-based Laves phase alloy with high capacity and high rate-capability for electro- This article based on a presentation made in the symposium “The 2nd KIM-JIM Joint Symposium: Hydrogen Absorbing Materials”, held at Hanyang University, Seoul, Korea, October 27-28, 2000 under the auspices of The Korean Institute of Metals and Materials and The Japan Institute of Metals.