D42.4 Secondary Batteries

Secondary batteries are rechargeable; that is, the reaction that powers the battery can be reversed so that the original reactants can be regenerated. Secondary batteries are found in smartphones, electronic tablets, automobiles, and many other devices.

Lead-Acid Battery

Lead-acid battery is the type of secondary battery used to start gasoline-powered automobiles. It is inexpensive and capable of producing the high current required by the starter motors when starting a car. They are heavy because of lead’s high density, contain highly corrosive concentrated sulfuric acid, and must be disposed of properly to avoid lead-poisoning hazards. But they can produce a lot of current in a short period of time so for certain applications they are the best choice.

The reactions occurring in a lead acid battery are:

Oxidation (anode): Pb(s) + HSO4–(aq) ⟶ PbSO4(s) + H+(aq) + 2e– E°anode = -0.359 V
Reduction (cathode): PbO2(s) + HSO4–(aq) + 3H+(aq) + 2e– ⟶ PbSO4(s) + 2H2O(ℓ) E°cathode = +1.690 V
overall: Pb(s) + PbO2(s) + 2H2SO4(aq) ⟶ 2PbSO4(s) + 2H2O(ℓ) E°cell = +2.049 V

Each cell produces 2.05 V, so six cells can be connected in series to produce a 12-V car battery.

A diagram of a lead acid battery is shown. A black outer casing, which is labeled “Protective casing” is in the form of a rectangular prism. Grey cylindrical projections extend upward from the upper surface of the battery in the back left and back right corners. At the back right corner, the projection is labeled “Positive terminal.” At the back right corner, the projection is labeled “Negative terminal.” The bottom layer of the battery diagram is a dark green color, which is labeled “H subscript 2 S O subscript 4.” A blue outer covering extends upward from this region near the top of the battery. Inside, alternating grey and white vertical “sheets” are packed together in repeating units within the battery. The battery has the sides cut away to show three of these repeating units which are separated by black vertical dividers, which are labeled as “cell dividers.” The grey layers in the repeating units are labeled “Negative electrode (lead).” The white layers are labeled “Postive electrode (lead dioxide).”
Figure: Lead-acid battery. The lead acid battery in an automobile consists of six cells connected in series to give 12 V. The low cost and high current output makes the battery suitable for providing power for a car’s starter motor.

In each cell, the lead electrodes are immersed in sulfuric acid. The anodes are spongy lead metal and the cathodes are lead impregnated with lead oxide. As the battery is discharged, a powder of PbSO4 forms on the electrodes. When a lead-acid battery is recharged by a car’s alternator, electrons are forced to flow in the opposite direction which reverses the reactions at anode and cathode, in other words, the cell undergoes electrolysis reactions to replenish the substances that have reacted away.

Practically, the concentrated sulfuric acid becomes quite viscous when the temperature is low, inhibiting the flow of ions between the plates and reducing the current that can be delivered. This effect is well-known to anyone who has had difficulty starting a car in cold weather. These batteries also tend to slowly self-discharge, so a car left idle for several weeks might be unable to start. And after thousands of discharge-charge cycles, PbSO4 that does not get converted to PbO2 gradually changes to an inert form which limits the battery capacity. Also, “fast” charging causes rapid evolution of potentially explosive H2 gas from the water in the electrolyte (electrolysis of water); the gas bubbles form on the lead surface and can tear PbO2 off the electrodes. Eventually enough solid material accumulates at the bottom of the electrolyte to short-circuit the battery, leading to its permanent demise.

Exercise: Lead-acid Batteries

Lithium Ion Battery

Lithium ion batteries are among the most popular rechargeable batteries and are used in many portable electronic devices because their advantages outweigh the disadvantage of higher cost. In a typical Li-ion battery the reactions are:

Oxidation (anode): LiCoO2 ⟶ Li1-xCoO2 + x Li+ + x e–
Reduction (cathode): x Li+ + x C6 + x e– ⟶ x LiC6
overall: LiCoO2 + x C6 ⟶ Li1-xCoO2 + x LiC6

(x is no more than about 0.5.) The battery voltage is about 3.7 V.

This figure shows a model of the flow of charge in a lithium ion battery. At the left, an approximately cubic structure formed by alternating red, grey, and purple spheres is labeled below as “Positive electrode.” The purple spheres are identified by the label “lithium.” The grey spheres are identified by the label “Metal.” The red spheres are identified by the label “oxygen.” Above this structure is the label “Charge” followed by a right pointing green arrow. At the right is a figure with layers of black interconnected spheres with purple spheres located in gaps between the layers. The black layers are labeled “Graphite layers.” Below the purple and black structure is the label “Negative electrode.” Above is the label “Discharge,” which is preceded by a blue arrow which points left. At the center of the diagram between the two structures are six purple spheres which are each labeled with a plus symbol. Three curved green arrows extend from the red, purple, and grey structure to each of the three closest purple plus labeled spheres. Green curved arrows extend from the right side of the upper and lower of these three purple plus labeled spheres to the black and purple layered structure. Three blue arrows extend from the purple and black layered structure to the remaining three purple plus labeled spheres at the center of the diagram. The base of each arrow has a circle formed by a dashed curved line in the layered structure. The lowest of the three purple plus marked spheres reached by the blue arrows has a second blue arrow extending from its left side which points to a purple sphere in the purple, green, and grey structure.
Figure: Lithium ion battery. In a lithium ion battery, charge flows between the electrodes as the lithium ions move between the anode and cathode.

Lithium batteries are popular because they can provide a large amount of current, are lighter than comparable batteries of other types, produce a nearly constant voltage as they discharge, and only slowly lose their charge when stored.

Exercise: Lithium-Ion Batteries

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Chemistry 109 Fall 2021 Copyright © by John Moore; Jia Zhou; and Etienne Garand is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License, except where otherwise noted.