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18.8:

Batteries and Fuel Cells

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Chemistry
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JoVE Core Chemistry
Batteries and Fuel Cells

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Batteries are voltaic cells used as portable electrical sources. They are categorized into primary, or non-rechargeable, and secondary, or rechargeable, batteries. The common primary battery is the dry cell. It contains a zinc case as the anode and a graphite cathode immersed in a moist, acidic electrolyte paste of manganese(IV) oxide and ammonium chloride.  The zinc oxidizes to zinc chloride, and manganese(IV) oxide reduces to solid manganese(III) oxide, generating a potential of 1.5 volts. When operated, the electrodes get depleted, making dry cells single-use batteries. Alkaline batteries are similar but use an alkaline electrolyte, extending their shelf and working lives. Lead-acid batteries are secondary batteries predominantly used in automobiles. These typically have six electrochemical cells connected in series, generating a total potential of 12 volts. Each cell has a lead anode and a lead oxide cathode immersed in sulfuric acid.  During discharge, the redox reactions deposit solid lead sulfate on both electrodes, which are converted back during recharging by using an external power source. Nickel–cadmium rechargeable batteries contain a nickel oxyhydroxide cathode, a cadmium anode, and a potassium hydroxide electrolyte. When operated, the anode oxidizes to solid cadmium hydroxide, and the cathode reduces to solid nickel hydroxide, generating a cell potential of 1.3 volts.  However, cadmium’s toxicity drives the replacement of nickel–cadmium batteries by eco-friendly nickel–metal hydride batteries. Here, the cathode remains the same, but the anode is a hydrogen-absorbing alloy. The anodic reaction involves the formation of water from hydrogen.  Lithium–ion batteries are the newest secondary batteries. Lightweight lithium metal makes these batteries portable with high energy density.  A lithium–ion battery contains a lithiated graphite anode and a lithium–transition metal oxide cathode. When charged, the transition metal is oxidized, while lithium ions are incorporated between the anodic graphite layers. Upon discharge, lithium ions flow from the anode to the cathode, generating a potential of 3.7 volts.  Lastly, fuel cells are voltaic cells that require a continuous external supply of redox reactants for energy production.  A typical hydrogen fuel cell uses hydrogen and oxygen from the air to generate a current while emitting water. Graphite electrodes contain platinum-based catalysts to accelerate the redox reaction.

18.8:

Batteries and Fuel Cells

A battery is a galvanic cell that is used as a source of electrical power for specific applications. Modern batteries exist in a multitude of forms to accommodate various applications, from tiny button batteries such as those that power wristwatches to the very large batteries used to supply backup energy to municipal power grids. Some batteries are designed for single-use applications and cannot be recharged (primary cells), while others are based on conveniently reversible cell reactions that allow recharging by an external power source (secondary cells).

Single-Use (Primary) Batteries

A dry-cell is a common primary battery that uses zinc as both the container and anode (“–” terminal) and a graphite rod as the cathode (“+” terminal). The Zn can is filled with an electrolyte paste containing manganese(IV) oxide, zinc(II) chloride, ammonium chloride, and water. A graphite rod is immersed in the electrolyte paste to complete the cell. The spontaneous cell reaction involves:

Eq1

The voltage (cell potential) of a dry cell is approximately 1.5 V (Ecell ~ 1.5 V). Dry cells are available in various sizes (e.g., D, C, AA, AAA). All sizes of dry cells comprise the same components and exhibit the same voltage, but larger cells contain greater amounts of the redox reactants and therefore are capable of transferring correspondingly greater amounts of charge. Like other galvanic cells, dry cells may be connected in series to yield batteries with greater voltage outputs, if needed. 

Alkaline batteries were designed around the same redox couples as the dry cell. As their name suggests, these types of batteries use alkaline electrolytes, often potassium hydroxide. The reactions are

Eq2

An alkaline battery can deliver about three to five times the energy of a dry cell of similar size (Ecell  = +1.43 V). Alkaline batteries are prone to leaking potassium hydroxide, so they should be removed from devices for long-term storage. While some alkaline batteries are rechargeable, most are not.

Rechargeable (Secondary) Batteries

Nickel-cadmium, or NiCd, batteries consist of a nickel-plated cathode, cadmium-plated anode, and a potassium hydroxide electrode. The positive and negative plates, which are prevented from shorting by the separator, are rolled together and put into the case. This design allows the NiCd cell to deliver much more current than a similar-sized alkaline battery. The reactions are

Eq3

When properly treated, a NiCd battery can be recharged about 1000 times ( Ecell ~ 1.3 V). Cadmium is a toxic heavy metal, so NiCd batteries should never be ruptured or incinerated, and they should be disposed of in accordance with relevant toxic waste guidelines.

Lithium-ion batteries are among the most popular rechargeable batteries and are used in many portable electronic devices. The reactions are

Eq4

The variable stoichiometry of the cell reaction leads to variation in cell voltages, but for typical conditions, x is usually no more than 0.5,and the cell voltage is approximately 3.7 V (Ecell ~ 3.7). 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.

The lead-acid battery is also a type of secondary battery commonly used in automobiles. It is inexpensive and capable of producing the high current required by automobile starter motors. The reactions for a lead-acid battery are

Eq5

Each cell produces 2 V (Ecell ~ 2 V), so six cells are connected in series to produce a 12-V car battery. Lead-acid batteries are heavy and contain a caustic liquid electrolyte, H2SO4 (aq), but are often still the battery of choice because of their high current density. Since these batteries contain a significant amount of lead, they must always be disposed of properly.

Fuel Cells

A fuel cell is a galvanic cell that uses traditional combustive fuels, most often hydrogen or methane, that are continuously fed into the cell along with an oxidant. Within the cell, fuel and oxidant undergo the same redox chemistry as when they are combusted, but via a catalyzed electrochemical that is significantly more efficient. For example, a typical hydrogen fuel cell uses graphite electrodes embedded with platinum-based catalysts to accelerate the two half-cell reactions:

Eq6

These types of fuel cells generally produce voltages of approximately 1.23 V (Ecell ~ 1.23 V). Compared to an internal combustion engine, the energy efficiency of a fuel cell using the same redox reaction is typically more than double (~20%–25% for an engine versus ~50%–75% for a fuel cell). Hydrogen fuel cells are commonly used on extended space missions, and prototypes for personal vehicles have been developed.

This text is adapted from Openstax, Chemistry 2e, Section 17.5: Batteries, and Fuel Cells.