Lead Acid Batteries

A lead acid battery consists of a negative electrode made of spongy or porous lead. The lead is porous to facilitate the formation and dissolution of lead. The positive electrode consists of lead oxide. Both electrodes are immersed in a electrolytic solution of sulfuric acid and water. In case the electrodes come into contact with each other through physical movement of the battery or through changes in thickness of the electrodes, an electrically insulating, but chemically permeable membrane separates the two electrodes. This membrane also prevents electrical shorting through the electrolyte. Lead acid batteries store energy by the reversible chemical reaction shown below.
The overall chemical reaction is:

At the negative terminal the charge and discharge reactions are:

At the positive terminal the charge and discharge reactions are:

As the above equations show, discharging a battery causes the formation of lead sulfate crystals at both the negative and positive terminals, as well as the release of electrons due to the change in valence charge of the lead. The formation of this lead sulfate uses sulfate from the sulfuric acid electrolyte surrounding the battery. As a result the electrolyte becomes less concentrated. Full discharge would result in both electrodes being covered with lead sulfate and water rather than sulfuric acid surrounding the electrodes. At full discharge the two electrodes are the same material, and there is no chemical potential or voltage between the two electrodes. In practice, however, discharging stops at the cutoff voltage, long before this point. The battery should not therefore be discharged below this voltage.
In between the fully discharged and charged states, a lead acid battery will experience a gradual reduction in the voltage. Voltage level is commonly used to indicate a battery's state of charge. The dependence of the battery on the battery state of charge is shown in the figure below. If the battery is left at low states of charge for extended periods of time, large lead sulfate crystals can grow, which permanently reduces battery capacity. These larger crystals are unlike the typical multicrystalline or porous structure of the lead electrode, and are difficult to convert back into lead.

Voltage of lead acid battery upon charging.

The charging reaction converts the lead sulfate at the negative electrode to lead. At the positive terminal the reaction converts the lead to lead oxide. As a by-product of this reaction, hydrogen is evolved. During the first part of the charging cycle, the conversion of lead sulfate to lead and lead oxide is the dominant reaction. However, as charging proceeds and most of the lead sulfate is converted to either lead or lead dioxide, the charging current electrolyzes the water from the electrolyte and both hydrogen and oxygen gas are evolved, a process known as the "gassing" of the battery. If current is being provided to the battery faster than lead sulfate can be converted, then gassing begins before all the lead sulfate is converted, that is, before the battery is fully charged. Gassing introduces several problems into a lead acid battery. Not only does the gassing of the battery raise safety concerns, due to the explosive nature of the hydrogen produced, but gassing also reduces the water in the battery, which must be manually replaced, introducing a maintenance component into the system. In addition, gassing may cause the shedding of active material from the electrolyte, thereby permanently reducing battery capacity. For these reasons, the battery should not regularly be charged above the voltage which causes gassing. The voltage across the battery and the gassing voltage are shown in the figure below.

Gassing voltage change with varying charge rates.

Lead sulphate is an insulator, and therefore the way in which lead sulfate forms on the electrodes determined how easily the battery can be discharged.
Self-discharge involves severn reactions. Give seperate reaction for H2 and O2 formation. Rate of oxygen evolution strongly influenced by imourties. Is O2 evolution a side reaction that contributes to self discharge? Anodic corrosion contributes to self-discharge. Negative self discharge is Pb + H2SO4 -> PbSO4 + H2. Formation of H2 gas is the slow step. High H2 overvoltage on lead, so process is slow with lead or lead calcium grids. Hoever, proceeds rapidly with SB. Sb Lowers O2 overvotlage. 1/2O2 + Pb+ H2SO4 -> PbSO$ + H20. IN open cells an issue. In closed cells can do an oxygen cylce.
Corrosion of lead and lead alloys. (what is reaction)