Cells operation

Heat produced in these cells operating at voltages of >2.31 V is generally removed by water evaporation and radiation losses. 

Electrolytic Cell Operating Characteristics. Currently the greatest volume of chlorine production is by the diaphragm ceU process, foUowed by that of the mercury ceU and then the membrane ceU. However, because of the ecological and economic advantages of the membrane process over the other systems, membrane ceUs are currently favored for new production facHities. The basic characteristics of the three ceU processes are shown in Eigure 5. 

The mercury cell operates efficiently because of the higher overpotential of hydrogen on mercury to achieve the preferential formation of sodium amalgam. Certain trace elements, such as vanadium, can lower the hydrogen overpotential, however, resulting in the release of hydrogen in potentially dangerous amounts. 

Catalytic cathodes in membrane cell operations exhibit a voltage savings of 100—200 mV and a life of about 2 + yr using ultrapure brine. However, trace impurities such as iron from the caustic recirculation loop can deposit on the cathode and poison the coating, thereby reducing its economic life. 

Cells operating at low (2,80,81) and high (79,82) temperatures were developed first, but discontinued because of corrosion and other problems. The first medium temperature cell had an electrolyte composition corresponding to KF 3HF, and operated at 65—75°C using a copper cathode and nickel anodes. A later cell operated at 75°C and used KF 2.2HF or KF 2HF as electrolyte (83,84), and nickel and graphite as anode materials. 

Molten Carbonate Fuel Cell. The electrolyte ia the MCFC is usually a combiaation of alkah (Li, Na, K) carbonates retaiaed ia a ceramic matrix of LiA102 particles. The fuel cell operates at 600 to 700°C where the alkah carbonates form a highly conductive molten salt and carbonate ions provide ionic conduction. At the operating temperatures ia MCFCs, Ni-based materials containing chromium (anode) and nickel oxide (cathode) can function as electrode materials, and noble metals are not required. 

As can be seen from Eigure 11b, the output voltage of a fuel cell decreases as the electrical load is increased. The theoretical polarization voltage of 1.23 V/cell (at no load) is not actually realized owing to various losses. Typically, soHd polymer electrolyte fuel cells operate at 0.75 V/cell under peak load conditions or at about a 60% efficiency. The efficiency of a fuel cell is a function of such variables as catalyst material, operating temperature, reactant pressure, and current density. At low current densities efficiencies as high as 75% are achievable. 

The lshi2uka cell (39—41), another multipolar cell that has been ia use by Showa Titanium (Toyama, Japan), is a cylindrical cell divided ia half by a refractory wall. Each half is further divided iato an electrolysis chamber and a metal collection chamber. The electrolysis chamber contains terminal and center cathodes, with an anode placed between each cathode pair. Several bipolar electrodes are placed between each anode—cathode pair. The cell operates at 670°C and a current of 50 kA, which is equivalent to a 300 kA monopolar cell. 

Table 1. Sodium Perchlorate Cell Operating Information 92-101.

The photogenerated current is in the same direction as /, but is always less than because the battier potential under load conditions is always less than F, which results in a larger flow of majority carriers than that in a short-circuited cell. Thus, when a solar cell is under load, the current and voltage are always less than and lU, respectively this condition is the curve-factor loss. Depending on the characteristics of the particularp—n junction and on the cell operating conditions, there is an optimal load resistance that maximizes the power output of the cell, ie, the product of its current and voltage. 

Alternating current is converted to direct current (dc) for the smelting cells by siUcon rectifiers. High conversion efficiency (over 99%) and minimum capital costs are achieved when the rectified voltage is 600—900 V dc. Because aluminum smelting cells operate at 4.5—5.0 V, 130 or more cells are coimected in series, forming what the industry calls a potline, which may operate at 50—360 kA. 

This process used an all-fluoride electrolyte, a portion of which was frozen on the carbon sidewalls to prevent short circuiting through the wads. One version of the cell operated at 20,000 A and 950—1000°C. The highest purity aluminum produced was 99.98%. A summary of the cell characteristics is given in Table 9. 

The cell bath in early Downs cells (8,14) consisted of approximately 58 wt % calcium chloride and 42 wt % sodium chloride. This composition is a compromise between melting point and sodium content. Additional calcium chloride would further lower the melting point at the expense of depletion of sodium in the electrolysis 2one, with the resulting compHcations. With the above composition, the cells operate at 580—600°C, well below the temperature of highest sodium solubiUty in the salt bath. Calcium chloride causes problems because of the following equiUbrium reaction (56) ... 

Sodium was made from amalgam ia Germany duriag World War II (68). The only other commercial appHcation appears to be the Tekkosha process (74—76). In this method, preheated amalgam from a chlor—alkali cell is suppHed as anode to a second cell operating at 220—240°C. This cell has an electrolyte of fused sodium hydroxide, sodium iodide, and sodium cyanide and an iron cathode. Operating conditions are given ia Table 6. 

The effect of the discharge rate is especially pronounced for the general purpose cells. On intermittent tests, the heavy-duty cell operates at high efficiency even at high rate. On continuous test at high rate, heavy-duty cells provide 60—70% of the intermittent service, whereas general purpose cells give only 30—50% of the intermittent service values. 

This reaction is accelerated by iacreased temperature, iacreased electrolyte concentration, and by the use of sodium hydroxide rather than potassium hydroxide ia the electrolyte. It is beheved that the presence of lithium and sulfur ia the electrode suppress this problem. Generally, if the cell temperature is held below 50°C, the oxidation and/or solubiUty of iron is not a problem under normal cell operating conditions. 

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