3"-alumina ZEBRA

The molten salt, sodium aluminum chloride, fulfills two other tasks in the cell system. The ceramic electrolyte "-alumina is sensitive to high-current spots. The inner surface of the ceramic electrolyte tube is completely covered with molten salt, leading to uniform current distribution over the ceramic surface. This uniform current flow is one reason for the excellent cycle life of ZEBRA batteries. 

The power of the ZEBRA cell depends on the resistance of the cell during discharge. The resistance of the ZEBRA cell rises with increasing depth of discharge (DOD). There is a contribution to the resistance from the fixed values of the solid metal components and of the/ "-alumina solid electrolyte. The variable parts of the resistance arc the sodium electrode and the positive electrode. The increase in internal resistance during discharge is almost entirely due to the positive electrode, as can be seen from Fig. 4. 

The ZEBRA cell shows the similar behavior during the charging reaction, in which the nickel is converted to nickel chloride within the reaction front. During the charging reaction the reaction front also moves from the / " -alumina into the positive electrode. 

The electrolyte / " -alumina has already been described in Chapter III, Sec. 9. This section relates to additional information on the manufacture of / "-alumina and its application and behavior in high-tem-perature batteries (ZEBRA and Na /S). 

The investigation of the stability of P -alumina in ZEBRA cells, which always contain some iron, showed an increase of resistance under certain extreme conditions of temperature (370 °C) and of voltage. This is related to the interaction of the P alumina with iron and it was shown that iron enters / -alumina in the presence of an electric field when current is passing, if the cell is deliberately overheated. However, it was found that only the P -phase but not the P"-phase was modified by the incursion of iron. The resistance of the iron-doped regions was high. It was shown that the addition of NaF inhibits access of the iron to the / " -alumina ceramic. By doping practical cells these difficulties have now been overcome and lifetime experiments show that the stability of / "-alumina electrolytes are excellent in ZEBRA cells. 

The high ionic conductivity of sodium (3"-alumina suggested that it would form a suitable electrolyte for a battery using sodium as one component. Two such cells have been extensively studied, the sodium-sulfur cell and the sodium-nickel chloride (ZEBRA) cell. The principle of the sodium-sulfur battery is simple (Fig. 6.13a). The (3"-alumina electrolyte, made in the form of a large test tube, separates an anode of molten sodium from a cathode of molten sulfur, which is contained in a porous carbon felt. The operating temperature of the cell is about 300°C. 

Figure 6.13 Batteries using p"-alumina electrolyte, schematic (a) the sodium-sulfur cell and (b) the sodium-nickel chloride (ZEBRA) cell.

Currently interest has now been directed toward a similar high temperature system, the ZEBRA Battery, which also uses P-alumina as a Na ion conductor. The sulfur electrode is replaced by nickel chloride or by a mixture of ferrous and nickel chlorides. Contact between the NiCl2 electrode and the solid electrolyte is poor as they are both solids, and current flow is improved by adding a second liquid electrolyte (molten NaAlCb) between this electrode and the P-alumina. The overall cell reaction is now ... 

One of the problems encountered with the Werth cell was an increase in resistance with cycling. This may have been caused in part by the /3-alumina reacting with the acidic sodium chloroaluminate melt. Coetzer had the idea of using transition metal chlorides as a positive electrode and chose a basic sodium chloroaluminate melt as the liquid electrolyte. This is compatible with /3-alumina, and a new class of secondary cells based upon the reaction between sodium metal and transition metal chloride has resulted from this work. Collectively, the term Zebra battery is used to describe this new class of cell. 

Another cleanup procedure of lipid extract (from zebra mussels) included first elution with 35 ml of hexane through a column packed with sodium sulfate, 1 g alumina and 2 g silica. Second elution was done with 15 ml of hexane through a 0.7 g silica column [88]. 

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 prospects of development of sodium ion batteries are very uncertain. The developers of such batteries remember the numerous efforts directed at the commercialization of batteries with a sodium negative electrode and ceramic electrolyte of P-alumina. Intensive development of batteries with the system of sodium-sulfur has been carried out since 1966 (for almost half a century ) and development of batteries with the system of sodium-nickel chloride (ZEBRA batteries) has been performed since 1978. It was assumed that these high-temperature batteries would form a basis for electric transport, but these systems are still referred to in the future tense. 

The ZEBRA cell, which is under development by the General Electric Co., uses a molten-sodium anode and a solid p,p"-alumina solid electrolyte as in the sodium-sulfur cell, but the positive electrode is large-surface-area nickel rather than molten sulfur with a large-surface-area current collector. The electrolyte on the cathode side of the ZEBRA solid electrolyte is an aqueous NaAlCLt containing NaCl and Nal as well as a little FeS. The FeS and Nal are added to limit growth of the Ni particles and to aid the overall cathode reaction, which is... 

ZEBRA battery is actually a Z E B R A (Zeolite Battery Research Africa) battery, that is, sodium-nickel chloride cell. This battery consists of a liquid Na negative electrode and NiCU separated by S-alumina solid electrolyte with Na" conduction. Total cell reaction is as follows ... 

ZEBRA Batteries, Fig. 1 Basic cell structure of ZEBRA battery. 1 Cell can for the Na negative electrode, 2 Na negative electrode, 3 ceramic electrode tube made of P-alumina, 4 mixture for the positive electrode (NiCl2 + NaAlCl4), 5 current collector for positive electrode, 6 thermal compression bond... 

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. 

Contacts. Usually, good mechanical contacts to a soHd are best accomphshed by a liquid. Examples are the sodium/suUur and the zebra batteries where the solid electrolyte acts as a separator between two Hquid phases. In the case of the zebra battery [6], an auxiliary electrolyte, NaAlCU (which is Hquid at the operating temperature of the battery), is employed to provide the contact between the solid sodium electrolyte, Na/j8" alumina, and the positive electrode, NiCh. It is especially difficult to prepare all-soHd-state batteries - except possibly thin-film batteries with good contacts - because of differences in the thermal expansion coefficients of the different materials and because the appHcation of high temperatures may result in undesirable side reactions including the evaporation of alkaline oxides. Employment of binders may minimize the mechanical contact problem but may increase the electrical resistance and may lead to slow reactions with the organic component of the binder. 

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