Lead Acid Batteries

A battery cell consists of two lead plates a positive plate covered with a paste of lead dioxide
and a negative made of sponge lead, with an insulating material (separator) in between. The
plates are enclosed in a plastic battery case and then submersed in an electrolyte consisting
of water and sulfuric acid.

A Lead-Acid Galvanic Cell Producing Electricity (discharging)

Discharge of a lead-acid cell:

 is a spontaneous redox reaction (E(redox) is positive)

 converts chemical energy stored in the lead, lead dioxide and sulfuric acid into electrical
energy

Below is a diagram of a lead-acid cell during discharge:

At the anode during discharge:

 Electrode: spongy lead, Pb(s) in a lead frame (porous lead plate)

Oxidation occurs ar the anode.

 Lead is oxidized at the anode:

Pb(s) → Pb2+(aq) + 2e-

 Pb2+ reacts with SO42- in sulfuric acid to produce PbSO4(s) as a precipitate:

Pb2+(aq) + SO42-(aq) → PbSO4(s)

PbSO4(s) sticks to the lead frame of the anode.

 The overall reaction at the anode is

Pb(s)+ SO42-(aq) → PbSO4(s)+ 2e-

 Electrons are produced at the anode.

 Anode is negative.
 Electrons migrate from anode (-) to cathode (+) along wires connecting the electrodes.

At the cathode during discharge:

 Electrode: lead frame covered with lead dioxide, PbO2(s)

 Reduction occurs at the cathode.
 Lead in lead dioxide is reduced at the cathode by protons from the sulfuric acid:

PbO2(s) + 4H+(aq) + 2e- → Pb2+(aq) + 2H2O(l)

 Pb2+ reacts with SO42- in sulfuric acid to produce PbSO4(s) as a precipitate:

Pb2+(aq) + SO42-(aq) → PbSO4(s)

PbSO4(s) sticks to the lead frame of the cathode.

 The overall reaction at the cathode is

PbO2(s) + 4H+(aq) + 2e- + SO42-(aq) → PbSO4(s) + 2H2O(l)

 Electrons are consumed at the cathode.

 Cathode is positive.
 Protons, H+(aq), are consumed at the cathode.

Wen can use the oxidation reaction at the anode and the reduction reaction that occurs at the
cathode to write an overall redox equation for the lead-acid cell:

anode
Pb(s) + SO42-(aq) → PbSO4(s)+ 2e-
reaction:

cathode
PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- → PbSO4(s) + 2H2O(l)
reaction:

overall
Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq) → 2PbSO4(s) + 2H2O(l) E ≈ +2 V
reaction:

As the lead-acid cell discharges:

 PbSO4 precipitates out and deposits on both the anode and the cathode.
 H+ from the electrolyte (H2SO4(aq)) is being used to produce water at the cathode.
+
 Concentration of H will be decreased over time (concentration of H2SO(aq) decreases).
 pH of the electrolyte (H2SO4(aq)) will increase.

Connecting lead-acid galvanic cells in a series to make lead-acid batteries allows us to make
batteries with voltages greater than 2 V:
 number of cells in series 2 3 4 5 6

approximate voltage 2×2=4 3×2=6 4×2=8 5 × 2 = 10 6 × 2 = 12

produced V V V V V

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Recharging a Lead-Acid Galvanic Cell

Recharging a lead-acid cell:

 is a non-spontaneous redox reaction (E(redox) is negative), that is, an electrolytic process

 requires an input of slightly more than 2 volts per cell to drive the spontaneous reactions in
the reverse direction
 converts electrical energy back into chemical energy which is stored in the lead, lead dioxide
and sulfuric acid in the cell

The diagram below shows a lead-acid cell during recharge:

cathode (-)

anode (+)

← e-

electrolyte

At the cathode during recharge:

 electrons are being pushed into the cathode from the recharger
 cathode is negative
 reduction occurs at the cathode
 lead in lead sulfate sticking to the electrode is reduced back to Pb(s):

PbSO4(s)+ 2e- → Pb(s)+ SO42-(aq)

At the anode during recharge:

 electrons are being pulled out of the anode by the recharger

 anode is positive
 oxidation occurs at the anode
 lead in lead sulfate sticking to the electrode is oxidized by water to reform lead dioxide:

PbSO4(s) + 2H2O(l) → PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-

 protons, H+, are produced at the anode

 electrons migrate from anode (+) to cathode (-)

Using the half-equations for the reactions occuring at the anode and cathode we can write
an overall redox reaction for the lead-acid cell during recharge:

cathode
PbSO4(s)+ 2e- → Pb(s) + SO42-(aq)
reaction:

anode
PbSO4(s) + 2H2O(l) → PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-
reaction:

overall
2PbSO4(s) + 2H2O(l) → Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq) E ≈ -2 V
reaction:

As the lead-acid cell recharges:

 PbSO4(s) on each electrode is removed.

+
 Concentration of H increases.
 pH of the electrolyte (H2SO4(aq)) decreases.

Recharging a lead-acid battery requires a minimum of 2 V per cell:

number of cells in series 2 3 4 5 6

recharge voltage required > 4 V > 6 V > 8 V > 10 V > 12 V

Overcharging a battery electrolyzes water, producing hydrogen gas and oxygen gas.

The bubbles of gas degrade the surfaces of the electrodes causing the PbSO4(s) to fall off the
electrodes.
This reduces the capacity of the cell.

Lead-acid battery Lead-acid battery is a type of secondary battery which uses a positive electrode of
brown lead oxide (sometimes called lead peroxide), a negative electrode of metallic lead and an
electrolyte of sulfuric acid (in either liquid or gel form). The overall cell reaction of a typical lead-acid
cell is:

The three major contributors to Lead-acid battery chemistry are lead, lead dioxide, and sulfuric acid.
Unfortunately pure lead is too soft to withstand the physical abuse; about 6% antimony is added to
strengthen it. Historically, antimony added to the lead grids, acted as a catalyst and made out
gassing (loss of hydrogen and oxygen during use) worse, and frequent water replenishing was
required. So battery manufacturers looked for another material that could strengthen the lead grids.
Calcium was added to both the positive and negative electrodes. It reduced out gassing enough to
allow manufacturers to claim they are building "maintenance-free batteries".