The degradation mechanism of MmNi,,,Co,,,Mn,4A1,, hydrogen storage alloy in nickel-metal hydride (Ni-MH) sealed batteries and effects of corrosion on cell performance during cycling are investigated. A general equation for the corrosion of AB, alloy is derived from analyses of corrosion products in cycled electrodes and measurements of negative discharge reserve. Water consumption due to alloy corrosion explains the increase of impedance during cycling while internal pressure evolution is directly linked to the loss of charge reserve. The parameters controlling the corrosion rate of AB, alloys are also examined. It is shown that the pulverization mode of the alloy particles rather than the surface reactivity to electrolyte explains the differences in cycle-life performance of alloys of various compositions.
InfrocluctionAmong different electrochemical systems, Ni-MH batteries are one of the most promising energy sources for cordless appliances and electric vehicles (EVs) because they are nonpolluting and have higher energy-storage capabilities than Ni-Cd batteries. The use of sealed Ni-MR batteries in ENs or mobile phones requires good stability of the impedance during the whole cycle life as well as a limited increase of internal pressure at the end of charge. These two characteristics can be achieved by using hydrogen storage alloys with low corrosion rates.The first purpose of this study was to measure corrosion rates of AB, alloys during cycling and evaluate the consequences of this corrosion on sealed Ni-MR battery performance. The second purpose was to determine the main parameters responsible for AB, corrosion and particularly to separate the effects of the reactivity of the surface and the decrepitation phenomenon (particle pulverization), which continuously generates new surfaces.
ExperimentalPreparation of alloy powders, electrodes, and cells.-Alloy ingots of composition MmNi,55Coai,Mn,4A1,, were prepared by melting Mm (Ce 50%, La 30%, Nd 15%, Pr 5%), Ni, Co, Mn, and Al in an induction furnace. After annealing, the ingots were mechanically ground into a powder of 35 jim in average diameter. A slurry containing metal hydride powder, a carbon black powder of high specific surface area, and styrene butadiene rubber was pasted into a foam nickel substrate. A carbon coating was then applied on the MR electrodes in order to improve their oxygen recombination ability. Positive electrodes were prepared by filling a nickel foam substrate with an active material consisting of Ni(OH), and cobalt compounds as conductive agents. Negative and positive electrodes as well as a polyamide separator were spirally wound to form cylindrical sealed cells (4/5 A size). Average capacity of the cells was 1.6 Ah at 1 C. The electrolyte was 8.7 M KOH-0.5 M NaOH-0.7 M LiOH.Electrical evaluation of the cells.-Cycle life was evaluated at room temperature using the following operating conditions: charge at 1 C for 1.2 h; discharge at I C to a cutoff potential of 0.9 V. Cells were periodically sampled for internal impedance, corrosion...