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Topics considered include: chemistry, experimental measurements, planar film model development, impregnation model development, results and conclusion. Also included: effect of cobalt concentration on deposition/loading; effect of current density on loading distribution.
Electrochemical experiments performed at sintered and bulk electrodes show that beta nickel hydroxide contains an electrochemically inactive proportion of cadmium hydroxide of up to 10%. The electrochemically ineffective cadmium hydroxide is homogeneously dissolved in beta nickel hydroxide.
Nickel hydroxide electrodes containing 11g/dsqm hydroxide, with capacities of 3.6 to 3.8 Ah/dsqm were prepared at 353 K by electrochemical impregnation. The reproducibility of the results is obtained by readjusting the pH before each preparation. The control of each electrode is done during two cycles of charge and discharge following the manufacture by a potential relaxation method.
Positive nickel hydroxide electrodes containing 20 mole percent of cobalt hydroxide are more efficient than when impregnated to the same degree by weight with nickel hydroxide alone. Charge-acceptance and oxygen-evolution tests indicate cobalt electrodes are more efficient than plain positive nickel hydroxide electrodes at all rates of charge.
Water contained in Ni hydroxide influences its electrochemical reactivity. The water content of alpha and beta Ni hydroxides is different with respect to the amount and bond strength. Thermogravimetric experiments show that the water of the beta Ni hydroxides exceeding the stoichiometric composition is completely removed at 160 deg. The water contained in the interlayers of the beta hydroxide, however, is removed only at higher temperatures, together with the water originating from the decomposition of the hydroxide. These differences are attributed to the formation of II bonds within the interlayers and between interlayers and adjacent main layers. An attempt is made to explain the relations between water content and the oxidizability of the Ni hydroxides.
Pure phases of some oxidized Ni oxides were prepared galvanimetrically with the Ni(2) hydroxide electrode of an alkaline battery. The crystallographic data of these phases, their chemical behavior, and conditions of transition were studied.
The electrochemical impregnation of nickel hydroxide in porous electrode was investigated both experimentally and theoretically. The loading level and plaque expansion were the most important parameters to be considered. The effects of applied current density, stirring, ratio of solution to electrode volume and pH were identified. A novel flow through electrochemical impregnation is proposed in which the electrolyte is forced through the porous nickel plaque. The thickening of the plaque can be reduced while maintaining high loading capacity. A mathematical model is presented which describes the transport of the nitrate, nickel and hydroxyl ions and the consecutive heterogeneous electrochemical reduction of nitrate and the homogeneous precipitation reaction of nickel hydroxide. The distributions of precipitation rate and active material within the porous electrode are obtained. A semiempirical model is also proposed which takes into account the plugging of the pores.
Including didymium hydrate in nickel hydroxide of positive electrode of storage batteries to increase ampere hour capacity
Spinel additives for nickel hydroxide electrodes to improve reversibility on charge and discharge
The effect of compression loads on positive nickel hydroxide electrodes is reported. Results show the electrodes could be compressed up to 20,000 kilograms without any change in capacity.
"Thermal-gradient mass transfer" was investigated in the molten sodium hydroxide-nickel system. Possible mechanisms (physical, electrochemical, and chemical) are discussed in terms of experimental and theoretical evidence. Experimental details are included in appendixes.
The various failure mechanisms were identified for the nickel electrode. The nickel sinter is involved in all these failure modes. The first one, chemical attack by carbonate, nitrate or other electrolyte components, involves corrosion of the nickel sinters. The second is the physical mode, which involves swelling of the electrode and physical shifting of the sinter in the electrodes. The third is the mechanical failure mode, and is due to fatigue or to the oxygen pressure that causes deformation or fracture of the sinter.
Mathematical models of alkaline rechargeable nickel cell systems (e.g., Ni-Cd, Ni-H(sub 2) and Ni-MH) have so far been developed based on the assumption that the active material at Ni electrode exists primarily in a single phase as Beta-NiOOH -- Beta-Ni(OH)(sub 2), despite enough experimental evidence for the second phase, i.e., Gamma-NiOOH -- Alpha-Ni(OH)(sub 2), especially under conditions of extended coverage. Here, we have incorporated the additional couple of Gamma-NiOOH -- Alpha-Ni(OH)(sub 2) into the modeling of the Ni electrode.
Conditioning is the initial cycling where cell capacity is usually unstable. The causes of the initial capacity build were examined. Gridless electrodes were fabricated to ensure mechanical homogeneity, so that a strain measured in one direction would be typical of a strain measured in the other directions. Plate hardness was also determined. These two parameters stabilize together.
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A nickel electrode having improved charging efficiency, an increased coefficient of discharging utilization, and large capacity is disclosed. Nickel hydroxide or nickel oxide is retained in a porous nickel substrate which is immersed in an aqueous solution of cobalt acetate with a pH 4.0 to 6.8. The electrode thus obtained is then immersed in an alkaline solution or heated to change cobalt acetate into cobalt hydroxide or cobalt oxide whereby the surface of nickel active material is covered with cobalt crystals and alloying of cobalt and nickel is promoted at the same time.
The use of the lightweight nickel electrode, in place of the heavy-sintered state-of-the-art nickel electrode, will lead to improvements in specific energy and performance of the nickel-hydrogen cell. Preliminary testing indicates that a nickel fiber mat is a promising support candidate for the nickel hydroxide active material. Nickel electrodes made from fiber mats, with nickel and cobalt powder added to the fiber, were tested at LeRC. To date, over 8000 cycles have been accumulated, at 40 percent depth-of-discharge, using the lightweight fiber electrode, in a boiler plate nickel-hydrogen cell.