Secondary electrolytes

The last type of nickel based battery here considered is the so-called sodium-nickel chloride or Zebra battery, firstly developed in 80s in Pretoria, South Africa (Zebra stands for ZEolite Battery Research Africa). The anode is made of liquid sodium, the electrolyte is based on sodium ion conducting -alumina and the cathode is constituted by nickel chloride. This is flooded with liquid NaAlCU which acts as a secondary electrolyte, i.e., its function is to enhance the transport of sodium ions from the solid nickel chloride to and from the alumina electrolyte [19]. They work at high temperature (157°C is the temperature necessary to have sodium in its molten state, but the better performance is obtained in the range 250-350°C) and operate with the following discharge semi- reactions at the anode ... 

The product of the primary plant was refined to pure Dj 0 in a small, nine-stage secondary plant, also operated with steady flow, but with the partially enriched hydrogen burned and recycled, as diown in Fig. 13.14. The secondary electrolytic plant has since been replaced by a water distillation plant. 

Details of the Manhattan District s secondary electrolytic plants are given by Maloney et al. [M8j. 

Figure 3.2 Pourbaix diagram (potential vs. pH) of Ti in a solution containing 2.5 M ZnBr2 (primary electrolyte) and 0.9 M ZnCl2 (secondary electrolyte), indicating stability...

Common supporting additives include potassium chloride and ammonium-based chlorides and bromides [8, 14]. These secondary electrolytes are usually added in smaller quantities than the main electrolyte and should be neutral salts in order to... 

The ZEBRA battery comprises a NiCU positive electrode in a central compartment with NaCl salt, impregnated with NaAlCls, which is a liquid mixture of NaCl and AICI3 (considered to be a secondary electrolyte). The negative electrode is liquid sodium confined in a second, outer compartment. The wall separating the two compartments is made of a P alumina ceramic (or P-AI2O3), conductive of sodium ions, considered to be the primary electrolyte. The element is sealed hermetically and functions at temperatures equal to or higher than 300°C so that the active components remain in the liquid state. 

Reliable failure mode—if the electrolyte fads, sodium will react with the secondary electrolyte to short-circuit the cell. 

The prime electrochemical difference between the two sodium-beta technologies is the sodium/metal-chloride positive electrode. This component contains a molten secondary electrolyte (NaAlClJ and an insoluble and electrochemically active metal-chloride phase (Fig. 40.1b). The secondary electrolyte is needed to conduct sodium ions from the primary /3"-AI2O3 electrolyte to the solid metal-chloride electrode. Cells using positive electrodes with two transition metal-chlorides, nickel and iron, have been developed. These specific metals were selected based on their insolubility in the molten NaAlCl4 secondary electrolyte. - During discharge, the solid metal-chloride is converted to the parent metal and sodium chloride crystals. The overall cell reactions for these two chemistries are as follows ... 

If the cell is overcharged, excess nickel chloride will be produced by the decomposition of the secondary electrolyte according to this reaction ... 

Finally, some limited attention has been given to appUeations other than electric vehicles. A number of years ago, development of sodium/nickel-chloride cells for aerospace applications was undertaken and, more recently, the use of this technology for powering submarines was evaluated. - The aerospace cells are essentially electric-vehicle cells with an optimized positive electrode and wicks for the sodium, and the secondary electrolyte that ensure operation in micro-g space environments. 

The interaction of an electrolyte with an adsorbent may take one of several forms. Several of these are discussed, albeit briefly, in what follows. The electrolyte may be adsorbed in toto, in which case the situation is similar to that for molecular adsorption. It is more often true, however, that ions of one sign are held more strongly, with those of the opposite sign forming a diffuse or secondary layer. The surface may be polar, with a potential l/, so that primary adsorption can be treated in terms of the Stem model (Section V-3), or the adsorption of interest may involve exchange of ions in the diffuse layer. 

Spain, Tmbia nea Oviedo 1972 spray chamber as primary roaster, plate reactor as secondary stage continuous electrolysis of filtered electrolyte, continuous crystallization 2,000 112... 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

Miscellaneous. Ruthenium dioxide-based thick-film resistors have been used as secondary thermometers below I K (92). Ruthenium dioxide-coated anodes ate the most widely used anode for chlorine production (93). Ruthenium(IV) oxide and other compounds ate used in the electronics industry as resistor material in apphcations where thick-film technology is used to print electrical circuits (94) (see Electronic materials). Ruthenium electroplate has similar properties to those of rhodium, but is much less expensive. Electrolytes used for mthenium electroplating (95) include [Ru2Clg(OH2)2N] Na2[Ru(N02)4(N0)0H] [13859-66-0] and (NH 2P uds(NO)] [13820-58-1], Several photocatalytic cycles that generate... 

Copper. Domestic mine production of copper metal in 1994 was over 1,800,000 t. Whereas U.S. copper production increased in the 1980s and 1990s, world supply declined in 1994. There are eight primary and five secondary smelters, nine electrolytic and six fire refiners, and fifteen solvent extraction—electro winning (SX—EW) plants. Almost 540,000 t/yr of old scrap copper and alloy are recycled in the United States accounting for - 24% of total U.S. consumption (11). New scrap accounted for 825,000 t of contained copper. Almost 80% of the new scrap was consumed by brass mills. The ratio of new-to-old scrap is about 60 40% representing 38% of U.S. supply. 

Electrolytic and distillation processes are used to produce primary slab zinc at smelters from ores and concentrates, whereas redistillation is used to recover zinc from secondary zinc materials at both primary and secondary smelters (see Table 13) (64,65). In 1965, neady 60% of the primary slab zinc was manufactured by the distillation process. However, in 1975, electrolytic slab zinc became dominant and by 1996 its share increased to 78%. 

When a battery produces current, the sites of current production are not uniformly distributed on the electrodes (45). The nonuniform current distribution lowers the expected performance from a battery system, and causes excessive heat evolution and low utilization of active materials. Two types of current distribution, primary and secondary, can be distinguished. The primary distribution is related to the current production based on the geometric surface area of the battery constmction. Secondary current distribution is related to current production sites inside the porous electrode itself. Most practical battery constmctions have nonuniform current distribution across the surface of the electrodes. This primary current distribution is governed by geometric factors such as height (or length) of the electrodes, the distance between the electrodes, the resistance of the anode and cathode stmctures by the resistance of the electrolyte and by the polarization resistance or hinderance of the electrode reaction processes. 

M. Klein and R. Costa, "Electrolytic Regenerative H2—O2 Secondary Fuel CeU," Proceedings of Space Technology Conference, ASME, June 1970. 

Electrolyte therefore plays three important roles increasing absorption in the neutral state, preventing desorption/promoting secondary exhaustion, and increasing the amount of ioni2ed ceHulose. Thus the amounts of salt used in the apphcation of fiber-reactive dyes are larger than for direct dyes. 

Seconday Current Distribution. When activation overvoltage alone is superimposed on the primary current distribution, the effect of secondary current distribution occurs. High overpotentials would be required for the primary current distribution to be achieved at the edge of the electrode. Because the electrode is essentially unipotential, this requires a redistribution of electrolyte potential. This, ia turn, redistributes the current. Therefore, the result of the influence of the activation overvoltage is that the primary current distribution tends to be evened out. The activation overpotential is exponential with current density. Thus the overall cell voltages are not ohmic, especially at low currents. 

Tertiay Current Distribution. The current distribution is again impacted when the overpotential influence is that of concentration. As the limiting current density takes effect, this impact occurs. The result is that the higher current density is distorted toward the entrance of the cell. Because of the nonuniform electrolyte resistance, secondary and tertiary current distribution are further compHcated when there is gas evolution along the cell track. Examples of iavestigations ia this area are available (50—52). 

Picolyl ethers are prepared from their chlorides by a Williamson ether synthesis (68-83% yield). Some selectivity for primary versus secondary alcohols can be achieved (ratios = 4.3-4.6 1). They are cleaved electrolytically ( — 1.4 V, 0.5 M HBF4, MeOH, 70% yield). Since picolyl chlorides are unstable as the free base, they must be generated from the hydrochloride prior to use. These derivatives are relatively stable to acid (CF3CO2H, HF/anisole). Cleavage can also be effected by hydrogenolysis in acetic acid. ... 

The tritylone ether is used to protect primary hydroxyl groups in the presence of secondary hydroxyl groups. It is prepared by the reaction of an alcohol with 9-phenyl-9-hydroxyanthrone under acid catalysis (cat. TsOH, benzene, reflux, 55-95% yield).It can be cleaved under the harsh conditions of the WolfT-Kishner reduction (H2NNH2, NaOH, 200°, 88% yield), " and by electrolytic reduction (-1.4 V, LiBr, MeOH, 80-85% yield). It is stable to 10% HCl, 55 h. ... 

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