NONRECHARGEABLE BATTERIES

(June, 2002)

Batteries - what would we do without them?

Fig. 1. Examples of commercial Leclanche cells from the 1960's. (Courtesy Eveready Battery Co., Inc.)

Fig. 2. Early "6-inch" cell. (Courtesy Eveready Battery Co., Inc.)

Let's talk about the smaller, portable kind, the ones you throw away when they don't run your toy or light your flashlight anymore. There are dozens of them, different sizes, different chemistries usually for different purposes (Figure 1). All these batteries, or more correctly, cells (if only one at a time), did not come into being all at once. In the 1880's and 1890's people needed something which would provide cheap reliable electricity even if they dropped the battery, threw it against the wall, or bounced along with it in an automobile over rough, unpaved roads. The batteries most in use then were so-called wet cells, electrodes in a ceramic or glass jar with liquid electrolyte. Some of these electrolyte solutions were corrosive and dangerous to handle. They could slosh around or pour out if the battery was overturned. The electrodes or internal contacts of batteries such as lead-acid batteries of the time sometimes would fall apart if subjected to very much jolting or vibration such as in an automobile on rough roads.

An electrical beginning

The earliest market was for dc power for experiments and for household door bells. Then Alexander Graham Bell chose these Leclanche "carbon" cells for use in his earliest long-distance demonstrations of the telephone. In addition about this time the spark-ignition gasoline engine started to appear on the national scene. The automobile engine and small farm engines needed a reliable source of electrical power to provide the spark for ignition of the gasoline in the cylinder(s) and in some cars to power the cranking of the engine to start it. Even if the engines were started with a crank, some had no generator to provide continuous power for the ignition to keep them going. The power for the spark was provided by a box of "six-inch" dry cells. (Although lead-acid batteries as used today were known and used, their short lifetime and the need for recharging, where there were few electric power lines, slowed their adoption as the only power source in the automobile.) The automobile and the telephone market consumed millions of these "six-inch" cells until the early nineteen twenties and some telephones in rural homes had them even after WW-II. The small farm engines revolutionized the farm economy and the automobile and the telephone revolutionized society. Critical to the success of these developments was the silent presence of these low cost "dry cells."
 

Flashlights and flashlight batteries

Fig. 3. Standard and heavy-duty Leclanche cells. (Courtesy Eveready Battery Co., Inc.)

A two pound (~one kg) Leclanche battery is a little large and heavy to carry around in one's pocket. Recognizing this, Conrad Hubert at the American Electrical Novelty and Manufacturing Company in 1898 and 1899 pioneered the use of the flashlight which was just that. It provided a relatively short flash of light for a time and then one waited for the batteries to recover. Two sizes of batteries were invented to power this type of device, "C" cells and "D" cells, as well as small light bulbs for the devices. It is said that the "C" cell is the diameter of a broom handle and the "D" cell is the diameter of a shovel handle. When the batteries and flashlights became popular, many more uses were found for the batteries and the industry grew rapidly with many companies and devices. The novelty company changed its name to American Ever Ready. The "D" and "C" batteries came to be made much like the more recent cells shown in Figure 3 but without the cell covers.
 

Radio batteries

Fig. 4. Flat Leclanche cell and battery assembly. (Courtesy Eveready Battery Co., Inc.)

In the 1920's the electronics of the "portable" radio became practical and the use of radios attractive. They were in general larger and heavier than portable radios of today. All sizes and combinations of Leclanche batteries were built to power these radios. Many of these batteries were stacks of flat, rectangular cells, (Figure 4), each consisting of a zinc piece (the anode), a coated paper separator to place between the zinc and the manganese-dioxide mixture, the mixture of manganese-dioxide ore, graphite and the usual Leclanche solution (an aqueous solution of ammonium-chloride salt and zinc-chloride salt). The zinc was painted with a conductive paint to act as the conductor of electrons on the manganese dioxide (cathode) side of the cell. The flat cells used the space of a battery box much more efficiently than round cells. These batteries allowed the use of radios, large and small, far from any electrical power line. The time in service of this and all similar batteries, flat or cylindrical, was greatly increased when a naturally occurring manganese-dioxide ore was discovered in the country of Ghana, Africa which performed much better in dry cells than manganese-dioxide ore used up to that time.
 

Higher energy batteries and World War II

Mercury batteries

Fig. 5. Cutaway view of a miniature manganese dioxide "button" cell. (Courtesy Eveready Battery Co., Inc.)

World War II brought great demands on the battery industry. Miniature batteries were needed to provide power in small devices including watches for the military. Samuel Ruben (an independent inventor) developed the zinc-mercuric oxide alkaline battery, licensed to the P.R. Mallory Co. (later Duracell, International). This battery gave five to eight times the service of a similar sized Leclanche battery. The cell was made in sizes as large as a "D" cell and yields a very reliable 1.35 volts on load rather than the constantly declining voltage of batteries with manganese-dioxide cathodes. Very few of these cells are produced now because of the manufacturing and disposal problems introduced by the presence of mercury or mercuric oxide. A modern "button" (or "coin") cell version is diagrammed in Figure 5.

Silver oxide batteries

Advances 1930 to 1960 for batteries with electrolytes based on water solutions (aqueous cells)

Leclanche cells

Zinc chloride "Heavy-Duty" cells

Alkaline zinc-manganese dioxide cells

Fig. 6. Cutaway view of a cylindrical alkaline cell. (Courtesy Eveready Battery Co., Inc.)

In the late 1940's several researchers recognized that, like silver-oxide cells, zinc-manganese dioxide cells could be made to function well with an alkaline electrolyte. In order to overcome the chemical reactivity of zinc in alkaline solutions the cells were made with six to eight percent of mercury amalgamated with the zinc to control its corrosion and hydrogen gas formation in the cells. When discharged or corroded rapidly, zinc tends to form a thick oxide layer on itself in alkaline solutions. Thus the zinc used was powdered to give it more surface on which to spread out the oxide in a very thin layer. In order to use this new zinc mass consisting of zinc powder and electrolyte, a polymer thickening agent was added to the electrolyte. In order to contain this mixture in the cells, the very dry manganese dioxide-graphite mixture was placed to the outside of the cell interior in the form of a tall annular ring and encased in a steel can. A separator and the zinc anode mixture were placed in the center of the ring and the basic cell was created just as is found today. The plastic and metal seal was clamped in the top of the steel can as a seal and closure with the brass contact to the zinc anode mass projecting through the seal. A jacket and covers were placed around the basic cell and can to contain the cell and allow the addition of attractive labels and shiny metal contact covers (Figure 6). Since the 1960's the mercury content of these alkaline cells has been replaced with other benign corrosion inhibitors. (As we consider this description it is important to note that this strong construction often contains pressure. The alkaline electrolyte is a very aggressive and dangerous chemical. The cells should not be cut apart except by trained, suitably protected technicians.)

An alkaline cell like this in the "D" size could provide more heavy drain service than the early "six-inch" cells which were nine times as large. This same "D" cell could give five to ten times as much service as low cost standard Leclanche cells of the same size. Of course they are more expensive to make but actually cost less per watt of electrical power delivered for the consumer.
 

Magnesium-manganese dioxide cells

Zinc-air (oxygen) cells

High energy batteries for the twenty first century

Lithium batteries with a solid cathode

Fig. 7. Lithium-manganese dioxide cell constructions: (a) miniature cell, (b) cylindrical cell. (Courtesy Eveready Battery Co., Inc.)

In the 1970's it became apparent that it was possible to make batteries with high-energy metals such as lithium. Lithium has an inherent voltage of 2.7 volts, enough to decompose water. Thus whatever the cathode material, the electrolyte needed to be of something besides a water solution. Such a battery and its non-water electrolyte is called a non-aqueous battery. Finding suitable mixtures of organic liquids and metal salts that were safe to use took many years. Out of this research came many different kinds of cells for all manner of applications from watches with tiny batteries to batteries large enough to power small cars. Cathode materials are varied but a special graphite with fluorine treatment and manganese dioxide are among the most common commercially for nonrechargeable cells. You can buy cylindrical lithium-manganese dioxide batteries in retail and electronics stores for especially cameras and similar devices (Figure 7). Another variation uses iron sulfide as the cathode. This powerful combination provides a 1.5 volt battery which can be directly substituted for alkaline or Leclanche (carbon-zinc) cells.

The manufacture of lithium cells and batteries is a high technology business. The cells must be assembled in rooms with relative humidity below three percent and preferably equal or less than one percent. Many major battery manufacturers have had serious factory fires when the materials of the batteries were unintentionally mishandled.
 

Lithium batteries with a liquid cathode

Zinc-air (oxygen) batteries

Future developments

Another area of great promise is the marriage of electronic internal devices and cell construction. Low cost microelectronic devices and cells similar to current product can be combined to modify battery performance in valuable ways especially for zinc-air cells. Otherwise one must look to fuel cells where the active chemicals are bought in little cylinders or packages and attached to the battery to in effect recharge a battery even though the active materials are used only once.

Related articles

Current density distribution in electrochemical cells
Flow batteries
Fuel cells
PEM fuel cells
Solid oxide cells
Volta and the "Pile"

Bibliography

• Handbook of Batteries (3^rd edition), D. Linden and T. B. Reddy (editors), McGraw-Hill, New York, 2001.

• Electrochemical Systems (2^nd edition), J. S. Newman, Prentice Hall, Englewood Cliffs, NJ, 1991.

• Modern Battery Technology, C. D. S. Tuck, Ellis Horwood, Chichester, UK, 1991.

• Twenty Five Years of Progress and Future Prospects (Proceedings of the 25^th Intersociety Energy Conversion Engineering Conference, Reno, NV, August 12-17, 1990, 6 volumes), P. A. Nelson, W. W. Schertz, and R. H. Till (editors), American Institute of Chemical Engineers, New York, 1990.

• Manganese Dioxide Electrode: Theory and Practice for Electrochemical Applications (From the 166^th Meeting of The Electrochemical Society, New Orleans, October 8-11, 1984, ECS Proceedings, Vol. 85-4), B. Schumm, R. L. Middaugh, M. P. Grotheer, and J. C. Hunter (editors), The Electrochemical Society, Pennington, NJ, 1985.

• Lithium Sulfur Dioxide Batteries, P. Bro and S. C. Levy, in "Lithium Battery Technology" pp 79-126, H. V. Venkatasetty (editor), Wiley, New York, 1984.

• Lithium Batteries, J.-P. Gabano (editor), Academic Press, New York, 1983.

• Small Batteries (two volumes), T. R. Crompton, Wiley, New York, 1982-1983.

• Electrochemical Power Sources, M. Barak (editor), Peter Peregrinus, New York, and Institution of Electrical Engineers, A. Wheaton and Co., Ltd. Exeter, UK, 1980.

• The Primary Battery (two volumes), N. C. Cahoon and G. H Heise (editors), Wiley, New York, 1971-1976.

• Batteries (Volume 1: Manganese Dioxide), K. V. Kordesch (editor), Marcel Dekker, New York, 1974.

• Electrochemical Kinetics, K. J. Vetter, Academic Press, New York, 1967.

• The Oxidation States of the Elements and Their Potentials in Aqueous Solutions (2^nd edition), W. M. Latimer, Prentice-Hall, New York, 1952.

• Fifth Letter on Voltaic Combinations, with some Account of the Effects of a large Constant Battery, J. F. Daniell, �Philosophical Transactions of the Royal Society of London� Vol. 129, pp 89-95, 1839. Available on the WWW.

• On Voltaic Combinations, J. F. Daniell, �Philosophical Transactions of the Royal Society of London� Vol. 126, pp 107-124, 1836. Available on the WWW.

• M�thode pratique pour exp�rimenter un �l�ment de pile, G. Leclanch�, �Comptes rendus hebdomadaires des s�ances de l'Acad�mie des sciences, Paris� Vol. 83, pp 1236-1238, 1876. Available on the WWW.

• Nouvelle pile au peroxyde de mangan�se, G. Leclanch�, �Comptes rendus hebdomadaires des s�ances de l'Acad�mie des sciences, Paris� Vol. 83, pp 54-56, 1876. Available on the WWW.

• G. Leclanch�, French Patents, No. 69,980 and 71,865, 1866.

• On the Electricity Excited by the Mere Contact of Conducting Substances of Different Kinds (in French), A. Volta, "Philosophical Transactions of the Royal Society of London" Vol. 90, pp 403-431, 1800. The original and a partial English translation are available on the WWW.

Listings of electrochemistry books, review chapters, proceedings volumes, and full text of some historical publications are also available in the Electrochemistry Science and Technology Information Resource (ESTIR). (http://knowledge.electrochem.org/estir/)

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