Density of Electrolyte. Discharge should be stopped when the density of the electrolyte, as measured with a hydrometer, is 1.150. When we pa.s.s a charging current through the battery, acid is produced by the chemical actions which take place in the plates. This gradually diffuses with the main electrolyte and causes the hydrometer to show a higher density than before. This increase in density continues steadily until the battery begins to "gas" freely.

The progress of the charge is generally determined by the density of the electrolyte. For this purpose in automobile batteries, a hydrometer is placed in a gla.s.s syringe having a short length of rubber tubing at one end, and a large rubber bulb at the other. The rubber tube is inserted in the cell and enough electrolyte drawn up into the syringe to float the hydrometer so as to be able to obtain a reading. This subject will be treated more fully in a later chapter.

Changes at Negative Plate. The charging current changes lead sulphate into spongy lead, and acid is formed. The acid is mixed with the diluted electrolyte outside of the plates. As the charging proceeds the active material shrinks or contracts, and the weight of the plate actually decreases on account of the difference between the weight and volume of the lead sulphate and spongy lead. If the cell has had only a normal discharge and the charge is begun soon after the discharge ended, the charge will proceed quickly and without an excessive rise in temperature. If, however, the cell has been discharged too far, or has been in a discharged condition for some time, the lead sulphate will not be in a finely divided state as it should be, but will be hard and tough and will have formed an insulating coating over the active material, causing the charging voltage to be high, and the charge will proceed slowly. When most of the lead sulphate has been reduced to spongy lead, the charging current will be greater than is needed to carry on the chemical actions, and will simply decompose the water into hydrogen and oxygen, and the cell "ga.s.ses." Spongy lead is rather tough and coherent, it, and the bubbles of gas which form in the pores of the negative plate near the end of the charge force their way to the surface without dislodging any of the active material.

Changes at the Positive Plate. When a cell has been discharged, a portion of the lead peroxide has been changed to lead sulphate, which has lodged in the pores of the active material and on its surface.

During charge, the lead combines with oxygen from the water to form lead peroxide, and acid is formed. This acid diffuses into the electrolyte as fast as the amount of sulphate will permit. If the discharge has been carried so far that a considerable amount of sulphate has formed in the pores and on the surface of the plate, the action proceeds very slowly, and unless a moderate charging current is used, ga.s.sing begins before the charge is complete, simply because the sulphate cannot absorb the current. The gas bubbles which originate in the interior of the plate force their way to the surface, and in so doing cause numerous fine particles of active material to break off and fall to the bottom of the jar. This happens because the lead peroxide is a granular, non-coherent substance, with the particles held together very loosely, and the gas breaks off a considerable amount of active material.

CHAPTER 7.

CAPACITY OF STORAGE BATTERIES.

The capacity of a storage battery is the product of the current drawn from a battery, multiplied by the number of hours this current flows.

The unit in which capacity is measured is the ampere-hour.

Theoretically, a battery has a capacity of 40 ampere hours if it furnishes ten amperes for four hours, and if it is unable, at the end of that time, to furnish any more current. If we drew only five amperes from this battery, it should be able to furnish this current for eight hours. Thus, theoretically, the capacity of a battery should be the same, no matter what current is taken from it. That is, the current in amperes, multiplied by the number of hours the battery, furnished this current should be constant.

In practice, however, we do not discharge a battery to a lower voltage than 1.7 per cell, except when the rate of discharge is high, such as is the case when using the starting motor, on account of the increasing amount of sulphate and the difficulty with which this is subsequently removed and changed into lead and lead peroxide. The capacity of a storage battery is therefore measured by the number of ampere hours it can furnish before its voltage drops below 1.7 per cell. This definition a.s.sumes that the discharge is a continuous one, that we start with a fully charged battery and discharge it continuously until its voltage drops to 1.7 per cell.

The factors upon which the capacity of storage batteries depend may be grouped in two main cla.s.sifications:

1. Design and Construction of Battery 2. Conditions of Operation

Design and Construction.

Each cla.s.sification may be subdivided. Under the Design and Construction we have:

(a) Area of plate surface.

(b) Quant.i.ty, arrangement, and porosity of active materials.

(c) Quant.i.ty and strength of electrolyte.

(d) Circulation of electrolyte.

These sub-cla.s.sifications require further explanation. Taking them in order:

(a) Area of Plate Surface. It is evident that the chemical and electrical activity of a battery are greatest at the surface of the plates since the acid and active material are in intimate contact here, and a supply of fresh acid is more readily available to replace that which is depleted as the battery is discharged. This is especially true with high rates of discharge, such as are caused in starting automobile engines. Therefore, the capacity of a battery will be greater if the surface area of its plates is increased. With large plate areas a greater amount of acid and active materials is available, and an increase in capacity results.

(b) Quant.i.ty, Arrangement, and Porosity of Active Materials. Since the lead and lead peroxide are changed to lead sulphate on discharge, it is evident that the greater the amount of these materials, the longer can the discharge continue, and hence the greater the capacity.

The arrangement of the active materials is also important, since the acid and active materials must be in contact in order to produce electricity. Consequently the capacity will be greater in a battery, all of whose active materials are in contact with the acid, than in one in which the acid reaches only a portion of the active materials.

It is also important that all parts of the plates carry the same amount of current, in order that the active materials may be used evenly. As a result of these considerations, we find that the active materials are supported on grids of lead, that the plates are made thin, and that they have large surface areas. For heavy discharge currents, such as starting motor currents, it is essential that there be large surface areas. Thick plates with smaller surface areas are more suitable for low discharge rates.

Since the inner portions of the active materials must have a plentiful and an easily renewable supply of acid, the active materials must be porous in order that diffusion may be easy and rapid.

(c) Quant.i.ty and Strength of Electrolyte. It is important that there be enough electrolyte in order that the acid may not become exhausted while there is still considerable active material left. An insufficient supply of electrolyte makes it impossible to obtain the full capacity from a battery. On the other hand, too much electrolyte, due either to filling the battery too full, or to having the plates in a jar that holds too much electrolyte, results in an increase in capacity up to the limit of the plate capacity. There is a danger present, however, because with an excess of electrolyte the plates will be discharged before the specific gravity of the electrolyte falls to 1.150. This results in over discharge of the battery with its attendant troubles as will be described more fully in a later chapter.

It is a universal custom to consider a battery discharged when the specific gravity of the electrolyte has dropped to 1.150, and that it is fully charged when the specific gravity of the electrolyte has risen to 1.280-1.300. This is true in temperate climates. In tropical countries, which may for this purpose be defined as those countries in which the temperature never falls below the freezing point, the gravity of a fully charged cell is 1.200 to 1.230. The condition of the plates is, however, the true indicator of charged or discharged condition. With the correct amount of electrolyte, its specific gravity is 1.150 when the plates have been discharged as far as it is considered safe, and is 1.280-1.300 when the plates are fully charged.

When electrolyte is therefore poured into a battery, it is essential that it contains the proper proportion of acid and water in order that its specific gravity readings be a true indicator of the condition of the plates as to charge or discharge, and hence show accurately how much energy remains in the cell at any time.

A question which may be considered at this point is why in automobile, work a specific gravity of 1.280-1.300 is adopted for the electrolyte of a fully charged cell. There are several reasons. The voltage of a battery increases as the specific gravity goes up. Hence, with a higher density, a higher voltage can be obtained. If the density were increased beyond this point, the acid would attack the lead grids and the separators, and considerable corrosion would result. Another danger of high density is that of sulphation, as explained in a later chapter. Another factor which enters is the resistance of the electrolyte. It is desirable that this be as low as possible. If we should make resistance measurements on various mixtures of acid and water, we should find that with a small percentage of acid, the resistance is high. As the amount of acid is increased, the resistance will grow less up to a certain point. Beyond this point, the resistance will increase again as more acid is added to the mixture.

The resistance is lowest when the acid forms 30% of the electrolyte.

Thus, if the electrolyte is made too strong, the plates and also the separators will be attacked by the acid, and the resistance of the electrolyte will also increase. The voltage increases as the proportion of acid is increased, but the other factors limit the concentration. If the electrolyte is diluted, its resistance rises, and the amount of acid is insufficient to give much capacity. The density of 1.280-1.300 is therefore a compromise between the various factors mentioned above.

(d) Circulation of Electrolyte. This refers to the pa.s.sing of electrolyte from one plate to another, and depends upon the ease with which the acid can pa.s.s through the pores of the separators. A porous separator allows more energy to be drawn from the battery than a nonporous one.

Operating Conditions.

Considering now the operating conditions, we find several items to be taken into account. The most important are:

(e) Rate of discharge.

(f) Temperature.

(e) Rate of Discharge. As mentioned above, the ampere hour rating of a battery is based upon a continuous discharge, starting with a specific gravity of 1.280-1.300, and finishing with 1.150. The end of the discharge is also considered to be reached when the voltage per cell has dropped to 1.7. With moderate rates of discharge the acid is abstracted slowly enough to permit the acid from outside the plates to diffuse into the pores of the plates and keep up the supply needed for the chemical actions. With increased rates of discharge the supply of acid is used up so rapidly that the diffusion is not fast enough to hold up the voltage. This fact is shown clearly by tests made to determine the time required to discharge a 100 Amp. Hr., 6 volt battery to 4.5 volts. With a discharge rate of 25 amperes, it required 160 minutes. With a discharge rate of 75 amperes, it required 34 minutes. From this we see that making the discharge rate three times as great caused the battery to be discharged in one fifth the time.

These discharges were continuous, however, and if the battery were allowed to rest, the voltage would soon rise sufficiently, to burn the lamps for a number of hours.

The conditions of operation in automobile work are usually considered severe. In starting the engine, a heavy current is drawn from the battery for a few seconds. The generator starts charging the battery immediately afterward, and the starting energy is soon replaced. As long as the engine runs, there is no load on the battery, as the generator will furnish the current for the lamps, and also send a charge into the battery. If the lamps are not used, the entire generator output is utilized to charge the battery, unless some current is furnished to the ignition system. Overcharge is quite possible.

When the engine is not running, the lamps are the only load on the battery, and there is no charging current. Various drivers have various driving conditions. Some use their starters frequently, and make only short runs. Their batteries run down. Other men use the starter very seldom, and take long tours. Their batteries will be overcharged. The best thing that can be done is to set the generator for an output that will keep the battery charged under average conditions.

From the results of actual tests, it may be said that modem lead-acid batteries are not injured in any way by the high discharge rate used when a starting motor cranks the engine. It is the rapidity with which fresh acid takes the place of that used in the pores of the active materials that affects the capacity of a battery at high rates, and not only limitation in the plates themselves. Low rates of discharge should, in fact, be avoided more than the high rates. Battery capacity is affected by discharge rates, only when the discharge is continuous, and the reduction in capacity caused by the high rates of continuous discharge does not occur if the discharge is an intermittent one, such as is actually the case in automobile work. The tendency now is to design batteries to give their rated capacity in very short discharge periods. If conditions should demand it, these batteries would be sold to give their rated capacity while operating intermittently at a rate which would completely discharge them in three or four minutes. The only change necessary for such high rates of discharge is to provide extra heavy terminals to carry the heavy current.

The present standard method of rating starting and lighting batteries, as recommended by the Society of Automotive Engineers, is as follows:

"Batteries for combined lighting and starting service shall have two ratings. The first shall indicate the lighting ability, and shall be the capacity in ampere hours of the battery when discharged continuously at the 5 hour rate to a final voltage of not less than 1.7 per cell, the temperature of the battery beginning such discharge being 80F. The second rating shall indicate the starting ability and shall be the capacity in ampere-hours when the battery is discharged continuously at the 20-minute rate to a final voltage of not less than 1.5 per cell, the temperature of the battery beginning such discharge being 80F."

The discharge rate required under the average starting conditions is higher than that specified above, and would cause the required drop in voltage in about fifteen minutes. In winter, when an engine is cold and stiff, the work required from the battery is even more severe, the discharge rate being equivalent in amperes to probably four or five times the ampere-rating of the battery. On account of the rapid recovery of a battery after a discharge at a very high rate, it seems advisable to allow a battery to discharge to a voltage of 1.0 per cell when cranking an engine which is extremely cold and stiff.

(f) Temperature. Chemical reactions take place much more readily at high temperatures than at low. Furthermore, the active materials are more porous, the electrolyte lighter, and the internal resistance less at higher temperatures. Opposed to this is the fact that at high temperatures, the acid attacks the grids and active materials, and lead sulphate is formed, even though no current is taken from the battery. Other injurious effects are the destructive actions of hot acid on the wooden separators used in most starting and lighting batteries. Greater expansion of active material will also occur, and this expansion is not, in general, uniform over the surface of the plates. This results in unequal strains and the plates are bent out of shape, or "buckled." The expansion of the active material will also cause much of it to fall from the plates, and we then have "shedding."

[Fig. 25 Graph: Theoretical temperature changes during charge and discharge]

When sulphuric acid is poured into water, a marked temperature rise takes place. When a battery is charged, acid is formed, and when this mixes with the diluted electrolyte, a temperature rise occurs. In discharging, acid is taken from the electrolyte, and the temperature has a tendency to drop. On charging, therefore, there is danger of overheating, while on discharge, excessive temperatures are not likely. Fig. 25 shows the theoretical temperature changes on charge and discharge. The decrease in temperature given-in the curve is not actually obtained in practice, because the tendency of the temperature to decrease is balanced by the heat caused by the current pa.s.sing through the battery.

Age of Battery.

Another factor which should be considered in connection with capacity is the age of the battery. New batteries often do not give their rated capacity when received from the manufacturer. This is due to the methods of making the plates. The "paste" plates, such as are used in automobiles, are made by applying oxides of lead, mixed with a liquid, which generally is dilute sulphuric acid, to the grids. These oxides must be subjected to a charging current in order to produce the spongy lead and lead peroxide. After the charge, they must be discharged, and then again charged. This is necessary because not all of the oxides are changed to active material on one charge, and repeated charges and discharges are required to produce the maximum amount of active materials. Some manufacturers do not charge and discharge a battery a sufficient number of times before sending it out, and after a battery is put into use, its capacity will increase for some time, because more active material is produced during each charge.

Another factor which increases the capacity of a battery after it is put into use is the tendency of the positive active material to become more porous after the battery is put through the cycles of charge and discharge. This results in an increase in capacity for a considerable time after the battery is put into use.

When, a battery has been in use for some time, a considerable portion of the active material will have fallen from the positive plates, and, a decrease in capacity will result. Such a battery will charge faster than a new one because the amount of sulphate which has formed when the battery is discharged is less than in a newer battery. Hence, the time required to reduce this sulphate will be less, and the battery will "come up" faster on charge, although the specific gravity of the electrolyte may not rise to 1.280.

CHAPTER 8.

INTERNAL RESISTANCE.