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Producing and Measuring Elecrical Quantities
Cells and Batteries

Section 1-2 Electrochemical Action


If a load (a device that consumes electrical power) is connected externally to the electrodes of a cell, electrons will flow under the influence of a difference in potential across the electrodes from the cathode (negative electrode), through the external conductor to the anode (positive electrode).

A cell is a device in which chemical energy is converted to electrical energy. This process is called electrochemical action.

The voltage across the electrodes depends upon the materials from which the electrodes are made and the composition of the electrolyte. The current that a cell delivers depends upon the resistance of the entire circuit, including that of the cell itself. The internal resistance of the cell depends upon the size of the electrodes, the distance between them in the electrolyte, and the resistance of the electrolyte. The larger the electrodes and the closer together they are in the electrolyte (without touching), the lower the internal resistance of the cell and the more current the cell is capable of supplying to the load.

Primary Cell Chemistry

When a current flows through a primary cell having carbon and zinc electrodes and a diluted solution of sulfuric acid and water (combined to form the electrolyte), the following chemical reaction takes place.

The current flow through the load is the movement of electrons from the negative electrode of the cell (zinc) and to the positive electrode (carbon). This causes fewer electrons in the zinc and an excess of electrons in the carbon. Figure 2-1 shows the hydrogen ions (H2) from the sulfuric acid being attracted to the carbon electrode. Since the hydrogen ions are positively charged, they are attracted to the negative charge on the carbon electrode. This negative charge is caused by the excess of electrons. The zinc electrode has a positive charge because it has lost electrons to the carbon electrode. This positive charge attracts the negative ions (S04) from the sulfuric acid. The negative ions combine with the zinc to form zinc sulfate. This action causes the zinc electrode to be eaten away. Zinc sulfate is a grayish-white substance that is sometimes seen on the battery post of an automobile battery.

The process of the zinc being eaten away and the sulfuric acid changing to hydrogen and zinc sulfate is the cause of the cell discharging. When the zinc is used up, the voltage of the cell is reduced to zero.

You can see in this figure that the zinc electrode is labeled negative and the carbon electrode is labeled positive. This represents the current flow outside the cell from negative to positive.

The zinc combines with the sulfuric acid to form zinc sulfate and hydrogen. The zinc sulfate dissolves in the electrolyte (sulfuric acid and water) and the hydrogen appears as gas bubbles around the carbon electrode. As current continues to flow, the zinc gradually dissolves and the solution changes to zinc sulfate and water. The carbon electrode does not enter into the chemical changes taking place, but simply provides a return path for the current.

Secondary Cell Chemistry

As stated before, the differences between primary and secondary cells are, the secondary cell can be recharged and the electrodes are made of different materials. The secondary cell, shown in the figure below, uses sponge lead as the cathode and lead peroxide as the anode. This is the lead-acid type cell and will be used to explain the general chemistry of the secondary cell. Later in the chapter when other types of secondary cells are discussed, you will see that the materials which make up the parts of a cell are different, but that the chemical action is essentially the same.

View A shows a lead-acid secondary cell that is fully charged. The cathode is pure sponge lead, the anode is pure lead peroxide, and the electrolyte is a mixture of sulfuric acid and water.

View B shows the secondary cell discharging. A load is connected between the cathode and anode; current flows negative to positive as shown. This current flow creates the same process as was explained for the primary cell with the following exceptions.

In the primary cell the zinc cathode was eaten away by the sulfuric acid. In the secondary cell the sponge-like construction of the cathode retains the lead sulfate formed by the chemical action of the sulfuric acid and the lead. In the primary cell the carbon anode was not chemically acted upon by the sulfuric acid. In the secondary cell the lead peroxide anode is chemically changed to lead sulfate by the sulfuric acid.

View C shows the cell when it is fully discharged. The anode and cathode retain some lead peroxide and sponge lead but the amounts of lead sulfate in each is maximum. The electrolyte has a minimum amount of sulfuric acid. With this condition no further chemical action can take place within the cell.

As you know, the secondary cell can be recharged. Recharging is the process of reversing the chemical action that occurs as the cell discharges. To recharge the cell, a voltage source, such as a generator, is connected as shown in figure 2-3 view D. The negative terminal of the voltage source is connected to the cathode of the cell and the positive terminal of the voltage source is connected to the anode of the cell. With this arrangement the lead sulfate is chemically changed back to sponge lead in the cathode, lead peroxide in the anode, and sulfuric acid in the electrolyte. After all the lead sulfate is chemically changed, the cell is fully charged as shown in view A. Once the cell has been charged, the discharge-charge cycle may be repeated.

Polarization of the Cell

The chemical action that occurs in the cell while the current is flowing causes hydrogen bubbles to form on the surface of the anode. This action is called polarization. Some hydrogen bubbles rise to the surface of the electrolyte and escape into the air, some remain on the surface of the anode. If enough bubbles remain around the anode, the bubbles form a barrier that increases internal resistance. When the internal resistance of the cell increases, the output current is decreased and the voltage of the cell also decreases.

A cell that is heavily polarized has no useful output. There are several methods to prevent polarization or to depolarize the cell.

One method uses a vent on the cell to permit the hydrogen to escape into the air. A disadvantage of this method is that hydrogen is not available to reform into the electrolyte during recharging. This problem is solved by adding water to the electrolyte, such as in an automobile battery. A second method is to use material that is rich in oxygen, such as manganese dioxide, which supplies free oxygen to combine with the hydrogen and form water.

A third method is to use a material that will absorb the hydrogen, such as calcium. The calcium releases hydrogen during the charging process. All three methods remove enough hydrogen so that the cell is practically free from polarization.

Local Action

When the external circuit is removed, the current ceases to flow, and, theoretically, all chemical action within the cell stops. However, commercial zinc contains many impurities, such as iron, carbon, lead, and arsenic. These impurities form many small electrical cells within the zinc electrode in which current flows between the zinc and its impurities. Thus, the chemical action continues even though the cell itself is not connected to a load.

Local action may be prevented by using pure zinc (which is not practical), by coating the zinc with mercury, or by adding a small percentage of mercury to the zinc during the manufacturing process. The treatment of the zinc with mercury is called amalgamating (mixing) the zinc. Since mercury is many times heavier than an equal volume of water, small particles of impurities weighing less than mercury will float to the surface of the mercury. The removal of these impurities from the zinc prevents local action.

The mercury is not readily acted upon by the acid. When the cell is delivering current to a load, the mercury continues to act on the impurities in the zinc. This causes the impurities to leave the surface of the zinc electrode and float to the surface of the mercury. This process greatly increases the storage life of the cell.

 

 

David L. Heiserman, Editor

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Revised: June 06, 2015