Electrodes nickel hydroxides

To prepare nickel oxide electrodes, nickel hydroxide precursors are frequently used, and nickel hydroxides are thermally oxidized to nickel oxide (Eig. 1). Industrially produced nickel hydroxide active materials are mainly used as... 

When nickel hydroxide is oxidized at the nickel electrode in alkaline storage batteries the black trivalent gelatinous nickel hydroxide oxide [12026-04-9], Ni(0H)0, is formed. In nickel battery technology, nickel hydroxide oxide is known as the nickel active mass (see Batteries, secondary cells). Nickel hydroxide nitrate [56171-41-6], Ni(0H)N02, and nickel chloride hydroxide [25965-88-2], NiCl(OH), are frequently mentioned as intermediates for the production of nickel powder in aqueous solution. The binding energies for these compounds have been studied (55). 

There are many methods of fabricating the electrodes for these cell systems. The eadiest commercially successhil developments used nickel hydroxide [12054-48-7] Ni(OH)2, positive electrodes. These electrodes are commonly called nickel electrodes, disregarding the actual chemical composition. Alkaline cells using the copper oxide—2inc couple preceeded nickel batteries but the CuO system never functioned well as a secondary battery. It was, however, commercially available for many years as a primary battery (see BatterieS-PRIMARY cells). 

Electrodes. A number of different types of nickel oxide electrodes have been used. The term nickel oxide is common usage for the active materials that are actually hydrated hydroxides at nickel oxidation state 2+, in the discharged condition, and nickel oxide hydroxide [12026-04-9] NiO OH, nickel oxidation state 3+, in the charged condition. Nickelous hydroxide [12034-48-7J, Ni(OH)2, can be precipitated from acidic solutions of bivalent nickel... 

The other type of nickel electrode involves constmctions in which the active material is deposited in situ. This includes the sintered-type electrode in which nickel hydroxide is chemically or electrochemically deposited in the pores of a 80—90% porous sintered nickel substrate that may also contain a reinforcing grid. 

Almost all the methods described for the nickel electrode have been used to fabricate cadmium electrodes. However, because cadmium, cadmium oxide [1306-19-0], CdO, and cadmium hydroxide [21041-95-2], Cd(OH)2, are more electrically conductive than the nickel hydroxides, it is possible to make simple pressed cadmium electrodes using less substrate (see Cadmium and cadmium alloys Cadmium compounds). These are commonly used in button cells. 

The nickel-cadmium battery was invented by Jungner in 1899. The battery used nickel hydroxide for the positive electrode, cadmium hydroxide for the negative electrode, and an alkaline solution for the electrolyte. Jungner s nickel-cadmium battery has undergone various forms of the development using improved materials and manufacturing processes to achieve a superior level of performance. 

Nickel hydroxides have been used as the active material in the positive electrodes of several alkaline batteries for over century [1], These materials continue to attract much attention because of the commercial importance of nickel-cadmium and nickel-metal hydride batteries. In addition to being the cathode active material in nickel-metal hydride batteries, Ni(OH)2 is an important corrosion product of the anode during cycling. There are several reviews of work in the field [2-10],... 

This section gives a brief overview of the structure of nickel hydroxide battery electrodes and a more detailed review of the solid-state chemistry and electrochemistry of the electrode materials. Emphasis is on work done since 1989. 

In normal battery operation several electrochemical reactions occur on the nickel hydroxide electrode. These are the redox reactions of the active material, oxygen evolution, and in the case of nickel-hydrogen and nickel-metal hydride batteries, hydrogen oxidation. In addition there are parasitic reactions such as the corrosion of nickel current collector materials and the oxidation of organic materials from separators. The initial reaction in the corrosion process is the conversion of Ni to Ni(OH)2. 

In acidic electrolytes only lead, because it forms passive layers on the active surfaces, has proven sufficiently chemically stable to produce durable storage batteries. In contrast, in alkaline medium there are several substances basically suitable as electrode materials nickel hydroxide, silver oxide, and manganese dioxide as positive active materials may be combined with zinc, cadmium, iron, or metal hydrides. In each case potassium hydroxide is the electrolyte, at a concentration — depending on battery systems and application — in the range of 1.15 - 1,45 gem"3. Several elec-... 

For alkaline storage batteries requirements are often demanded exceeding by far those for lead storage batteries. The reason is that the suitable materials for the positive electrode are very expensive (silver oxide, nickel hydroxide) and thus the use of these storage batteries is only justified where requirements as to weight, number of cycles, or temperature range prohibit other solutions. Besides a few standardized versions — mainly for nickel-cadmium batteries — this has led to the existence of a large diversity of constructions for special applications [4-6, 108, 109],... 

Oxidation of Organic Compounds at the Nickel Hydroxide Electrode H.-J. Schafer... 

Sandorfy, C. Vibrational Spectra of Hydrogen Bonded Systems in the Gas Phase. 120, 41-84 (1984). Schafer, H.-J. Oxidation of Organic Compounds at the Nickel Hydroxide Electrode. 142, 101-129 (1987). 

Mixing of the electrode products causes hydrolytic precipitation of the nickel and, after separation of the nickel hydroxide, the filtrate was returned to the cells. The sequence of the electrolytic purification steps is outlined in Figure 6.28. Nickel hydroxide slurry is first added to the anolyte for the purpose of raising the pH to 3.7 (2 H+ + Ni(OH) = Ni2+ + 2 H20), and iron(II) is oxidized by introducing chlorine. This causes hydrolytic precipitation of the iron(III) and corrects the nickel ion deficiency by the low anodic current efficiency. The iron(III) hydroxide is removed by filteration. The clarified solution is then treated with nickel carbonate and further chlorine to oxidize the cobalt(II) and allow its separation as cobalt(I II) hydroxide. 

First of all let us consider the morphological structure of an agglomerate electrode [6] by way of example of the model shown in Figure 1. This schematic represents a multiphase system with no fixed connection between its components. As a rule, the active mass of an electrode is a mixture of Nickel hydroxide (oxyhydroxide) with conductive carbon or a metal, which are well dispersed mechanically in the matrix. 

Micka K., Rousar I. Theory of Porous Electrodes. XVI. The Nickel Hydroxide Electrode. Electrochim. Acta. 1980 25 1085-90. 

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