CHAPTER 5
WHAT TAKES PLACE DURING DISCHARGE
Considered chemically, the discharge of a storage battery consists of the changing of the spongy lead and lead peroxide into lead sulphate, and the abstraction of the acid from the electrolyte. Considered electrically, the changes are more complex, and require further investigation. The voltage, internal resistance, rate of discharge, capacity, and other features must be considered, and the effects of changes in one upon the others must be studied. This proceeding is simplified considerably if we consider each point separately. The abstraction. of the acid from the electrolyte gives us a method of determining the condition of charge or discharge in the battery, and must also be studied.
Voltage Changes During Discharge. At the end of a charge, and before opening the charging circuit, the voltage of each cell is about 2.5 to 2.7 volts. As soon as the charging circuit is opened, the cell voltage drops rapidly to about 2.1 volts, within three or four minutes. This is due to the formation of a thin layer of lead sulphate on the surface of the negative plate and between the lead peroxide and the metal of the positive plate. Fig. 21 shows how the voltage changes during the last eight minutes of charge, and how it drops rapidly as soon as the charging circuit is opened. The final value of the voltage after the charging circuit is opened is about 2.15-2.18 volts. This is more fully explained in Chapter 6. If a current is drawn from the battery at the instant the charge is stopped, this drop is more rapid. At the beginning of the discharge the voltage has already had a rapid drop from the final voltage on charge, due to the formation of sulphate as explained above. When a current is being drawn from the battery, the sudden drop is due to the internal resistance of the cell, the formation of more sulphate, and the abstracting of the acid from the electrolyte which fills the pores of the plate. The density of this acid is high just before the discharge is begun. It is diluted rapidly at first, but a balanced condition is reached between the density of the acid in the plates and in the main body of the electrolyte, the acid supply in the plates being maintained at a lowered density by fresh acid flowing into them from the main body of electrolyte. After the initial drop, the voltage decreases more slowly, the rate of decrease depending on the amount of current drawn from the battery. The entire process is shown in Fig. 22.
Lead sulphate is being formed on the surfaces, and in the body of the plates. This sulphate has a higher resistance than the lead or lead peroxide, and the internal resistance of the cell rises, and contributes to the drop in voltage. As this sulphate forms in the body of the plates, the acid is used up. At first this acid is easily replaced from the main body of the electrolyte by diffusion. The acid in the main body of the electrolyte is at first comparatively strong, or concentrated, causing a fresh supply of acid to flow into the plates as fast as it is used up in the plates. This results in the acid in the electrolyte growing weaker, and this, in turn, leads to a constant decrease in the rate at which the fresh acid flows, or diffuses into the plates. Furthermore, the sulphate, which is more bulky than the lead or lead peroxide fills the pores in the plate, making it more and more difficult for acid to reach the interior of the plate. This increases the rate at which the voltage drops.The sulphate has another effect. It forms a cover over the active material which has not been acted upon, and makes it practically useless, since the acid is almost unable to penetrate the coating of sulphate. We thus have quantities of active material which are entirely enclosed in sulphate, thereby cutting down the amount of energy which can be taken from the battery. Thus the formation of sulphate throughout each plate and the abstraction of acid from the electrolyte cause the voltage to drop at a constantly increasing rate.
Theoretically, the discharge may be continued until the voltage drops to zero, but practically, the discharge should be stopped when the voltage of each cell has dropped to 1.7 (on low discharge rates). If the discharge is carried on beyond this point much of the spongy lead and lead peroxide have either been changed into lead sulphate, or have been covered up by the sulphate so effectively that they are almost useless. Plates in this condition require a very long charge in order to remove all the sulphate.
The limiting value of 1.7 volts per cell applies to a continuous discharge at a moderate rate. At a very high current flowing for only a very short time, it is not only' safe, but advisable to allow a battery to discharge to a lower voltage, the increased drop being due to the rapid dilution of the acid in the plates.
The cell voltage will rise somewhat every time the discharge is stopped. This is due to the diffusion of the acid from the main body of electrolyte into the plates, resulting in an increased concentration in the plates. If the discharge has been continuous, especially if at a high rate, this rise in voltage will bring the cell up to its normal voltage very quickly on account of the more rapid diffusion of acid which will then take place.
The voltage does not depend upon the area of the plate surface but upon the nature of the active materials and the electrolyte. Hence, although the plates of a cell are gradually being covered with sulphate, the voltage, measured when no current is flowing, will fall slowly and not in proportion to the amount of energy taken out of the cell. It is not until the plates are pretty thoroughly covered with sulphate, thus making it difficult for the acid to reach the active material, that the voltage begins to drop rapidly. This is shown clearly in Fig. 22, which shows that the cell voltage has dropped only a very small amount when the cell is 50% discharged. With current flowing through the cell, however, the increased internal resistance causes a marked drop in the voltage. Open circuit voltage is not useful, therefore to determine how much energy has been taken from the battery.
Acid Density. The electrolyte of a lead storage battery is a mixture of chemically pure sulphuric acid, and chemically pure water, the acid forming about 30 per cent of the volume of electrolyte when the battery is fully charged. The pure acid has a "specific gravity" of 1.835, that is, it is 1.835 times as heavy as an equal volume of water. The mixture of acid and water has a specific gravity of about 1.300. As the cell discharges, acid is abstracted from the electrolyte, and the weight of the latter must therefore grow less, since there will be less acid in it. The change in the weight, or specific gravity of the electrolyte is the best means of determining the state of discharge of a cell, provided that the cell has been used properly. In order that the value of the specific gravity may be used as an indication of the amount of energy in a battery, the history of the battery must be known. Suppose, for instance, that in refilling the battery to replace the water lost by the natural evaporation which occurs in the use of a battery, acid, or a mixture of acid and water has 'been used. This will result in the specific gravity being too high, and the amount of energy in the battery will be less than that indicated by the specific gravity. Again, if pure water is used to replace electrolyte which has been spilled, the specific gravity will be lower than it should be. In a battery which has been discharged to such an extent that much of the active material has been covered by a layer of tough sulphate, or if a considerable amount of sulphate and active material has been loosened from the plates and has dropped to the bottom of the cells, it will be impossible to bring the specific gravity of the electrolyte up to 1.300, even though a long charge is given. There. must, therefore, be a reasonable degree of certainty that a battery has been properly handled if the specific gravity readings are to be taken as a true indication of the condition of a battery. Where a battery does not give satisfactory service even though the specific gravity readings are satisfactory, the latter are not reliable as indicating the amount of charge in the battery.
As long as a discharge current is flowing from the battery, the acid within the plates is used up and becomes very much diluted. Diffusion between the surrounding electrolyte and the acid in the plates keeps up the supply needed in the plates in order to, carry on the chemical changes. When the discharge is first begun, the diffusion of acid into the plates takes place rapidly because there is little sulphate clogging the pores in the active material, and because there is a greater difference between the concentration of acid in the electrolyte and in the plates than will exist as the discharge progresses. As the sulphate begins to form and fill up the pores of the plates, and as more and more acid is abstracted from the electrolyte, diffusion takes place more slowly.
If a battery is allowed to stand idle for a short time after a partial discharge, the specific gravity of the electrolyte will decrease because some, of the acid in the electrolyte will gradually flow into the pores of the plates to replace the acid used up while the battery was discharging. Theoretically the discharge can be continued -until all the acid has been used up, and the electrolyte is composed of pure water. Experience has shown, however, that the discharge of the battery should not be continued after the specific gravity of the electrolyte has fallen to 1.150. As far as the electrolyte is concerned, the discharge may be carried farther with 'safety. The plates determine the point at which the discharge should be stopped. When the specific gravity has dropped from 1.300 to 1.150, so much sulphate has been formed that it fills the pores in the active material on the plates. Fig. 23 shows the change in the density of the acid during discharge.
Changes at the Negative Plate. Chemically, the action at the negative plate consists only of the formation of lead sulphate from the spongy lead. The lead sulphate is only slightly soluble in the electrolyte and is precipitated as soon as it is formed, leaving hydrogen ions, which then go to the lead peroxide plate to form water with oxygen ions released at the peroxide plate. The sulphate forms more quickly on the surface of the plate than in the inner portions because there is a constant supply of acid available at the surface, whereas the formation of sulphate in the interior of the plate requires that acid diffuse into the pores of the active materials to replace that already used up in the formation of sulphate. In the negative plate, however, the sulphate tends to form more uniformly throughout the mass of the lead, because the spongy lead is more porous than the lead peroxide, and because the acid is not diluted by the formation of water as in the positive plate.Changes at the, Positive Plate. In a fully charged positive plate we have lead peroxide as the active material. This is composed of lead and oxygen. From this fact it is plainly evident that during discharge there is a greater chemical activity at this plate than at the negative plate, since we must find something to combine with the oxygen in order that the lead may form. lead sulphate with the acid. In an ideal cell, therefore, the material which undergoes the greater change should be more porous than the material which does not involve as great a chemical reaction. In reality, however, the peroxide is not as porous as the spongy lead, and does not hold together as well.
The final products of the discharge of a positive plate are lead sulphate and water. The lead peroxide must first be reduced to lead, which then combines with the sulphate from the acid to form lead sulphate, while the oxygen from the peroxide combines with the hydrogen of the acid to form water. There is, therefore, a greater activity at this plate than at the lead plate, and the formation of the water dilutes the acid in and around the plate so that the tendency is for the chemical actions to be retarded.
The sulphate which forms on discharge causes the active material to bulge out because it occupies more space than the peroxide. This causes the lead peroxide at the surface to begin falling, to the bottom of the jar in fine dust-like particles, since the peroxide here holds together very poorly.
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