Positive electrode batteries

Fig. 2. Standard potentials of battery (a) negative electrode and (b) positive electrode reactions (13). Potentials are given in volts.

Cell geometry, such as tab/terminal positioning and battery configuration, strongly influence primary current distribution. The monopolar constmction is most common. Several electrodes of the same polarity may be connected in parallel to increase capacity. The current production concentrates near the tab connections unless special care is exercised in designing the current collector. Bipolar constmction, wherein the terminal or collector of one cell serves as the anode and cathode of the next cell in pile formation, leads to gready improved uniformity of current distribution. Several representations are available to calculate the current distribution across the geometric electrode surface (46—50). 

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). 

Nickel—2iiic batteries containing a vibrating zinc anode lias been reported (83). In this system zinc oxide active material is added to the electrol 1 e as a slurry. During charge the anode substrates are vibrated and the zinc is electroplated onto the surface in a unifomi mamier. Tlie stationary positive electrodes (nickel) are encased in a thin, open plastic netting which constitutes the entire separator system. 

The mercurous sulfate [7783-36-OJ, Hg2S04, mercury reference electrode, (Pt)H2 H2S04(y ) Hg2S04(Hg), is used to accurately measure the half-ceU potentials of the lead—acid battery. The standard potential of the mercury reference electrode is 0.6125 V (14). The potentials of the lead dioxide, lead sulfate, and mercurous sulfate, mercury electrodes versus a hydrogen electrode have been measured (24,25). These data may be used to calculate accurate half-ceU potentials for the lead dioxide, lead sulfate positive electrode from temperatures of 0 to 55°C and acid concentrations of from 0.1 to Sm. 

Some battery designs have a one-way valve for pressure rehef and operate on an oxygen cycle. In these systems the oxygen gas formed at the positive electrode is transported to the negative electrode where it reacts to reform water. Hydrogen evolution at the negative electrode is normally suppressed by this reaction. The extent to which this process occurs in these valve regulated lead —acid batteries is called the recombination-efficiency. These processes are reviewed in the Hterature (50—52). 

PbO TbSO H20. If the temperature is elevated to >57° C, the result is coarse tetrabasic lead sulfate, 4PbO TbSO, crystals. This is especially critical for the positive electrode where tribasic sulfate converts readily to Pb02 during battery formation but tetrabasic sulfate does not (93). 

The most important rechargeable lithium batteries are those using a soHd positive electrode within which the lithium ion is capable of intercalating. These intercalation, or insertion, electrodes function by allowing the interstitial introduction of the LE ion into a host lattice (16,17). The general reaction can be represented by the equation ... 

A battery system closely related to Na—S is the Na—metal chloride cell (70). The cell design is similar to Na—S however, ia additioa to the P-alumiaa electrolyte, the cell also employs a sodium chloroalumiaate [7784-16-9J, NaAlCl, molten salt electrolyte. The positive electrode active material coasists of a transitioa metal chloride such as iroa(Il) chloride [7758-94-3] EeQ.25 or nickel chloride [7791-20-0J, NiQ.25 (71,72) in Heu of molten sulfur. This technology is in a younger state of development than the Na—S. 

The external circuit provides a path for the excess electrons at the negative electrode to move toward the positive electrode. Although the flow of electrons would seem to cancel out the two charges, chemical processes in the battery build the charges up as fast as the depletion rate. When the electrodes can no longer pass electrons between them, the battery dies. ... 

The discharge of alkaline-manganese batteries comes from the electrochemical reactions at the anode and cathode. During discharge, the negative electrode material, zinc, is oxidized, forming zinc oxide at the same time, Mn02 in the positive electrode is reduced (MnOOH) ... 

The nickel-cadmium battery [6] has a positive electrode made of nickel hydrox-... 

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. 

For many years, sintered-nickel electrodes have been used as the positive electrodes for sealed-type nickel-cadmium batteries. With an increase in the demand for high energy density, this type of elec-... 

These batteries incorporate a polyacenic semiconductor (PAS) for the active material of the positive electrode, lithium for that of the negative electrode and an organic solvent for the electrolyte. PAS is essentially amorphous with a rather loose structure of molecular-size order with an interlayer distance of 4.0 A, which is larger than the 3.35 A of graphite [56, 57]. 

These batteries are new systems which use a lithium-manganese composite oxide for the active material of the positive electrode a lithium-titanium oxide with a spinel... 

As mentioned above, the typical positive electrode material is LiCo02, and there are typically two types of negative electrode materials, such as coke and graphite. The characteristics of lithium-ion batteries constructed using these electrode materials are discussed below. 

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],... 

---