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The beginning

In 1800, Alessandro Volta (1745-1827) designed a device that was able to constantly produce electric current. In the same year William Nicholson (1753-1815) and Antony Carlisle (1768-1840) performed the first experiment to decompose water with a Volta column, in which electric current was used to produce hydrogen and oxygen from water. What we are interested in is the reverse process, i.e., the combination of hydrogen and oxygen to form water:

The synthesis of hydrogen and oxygen

2H₂(gas) + O₂ (gas) →2H₂O (liquid)

This is called exploding gas reaction, since it takes place very fiercely, with a big energy release, only by a certain H₂/O₂ proportion (> 2) and at a temperature higher than 600 °C. In the presence of platinum catalyst H₂ and O₂ mix explosively.

 

Accidents helped a lot here as well…

Sir William Robert Grove

Sir William Robert Grove (1811-1896), considered as the father of fuel cells, realized that the above reaction can be used for energy production in a galvanic battery with high efficiency even at room temperature. In 1838, during the electrolysis of water he noticed that after switching off the electric current, a current begins to flow in the opposite direction.

The reason for this current is the following. The hydrogen produced on one of the platinum electrodes is oxidized, while the oxygen on the other electrode is reduced. On the base of this discovery, Grove constructed the first fuel cell, which he called gas battery to distinguish it from other batteries in which a reaction between metals and metal compounds produced the current. A gas battery consists of two platinum electrodes with one end of each immersed in sulfuric acid. The other ends separately sealed in containers of oxygen and hydrogen. Grove noticed that the level of the solutions rises when current flows between the two electrodes. This indicated the consumption of the hydrogen and oxygen. Grove wanted to create a competitor for the steam engine, but without success, at least in his life.

 

The theory gave the answers only later…

It is written that for more than 100 years after Grove nothing happened in the respect of the utilization of fuel cells. This is partly true. Indeed, this significant invention was not exploited, but there were continuous attempts to do so. F.W. Ostwald theoretically explained the processes taking place in fuel cells (1893), while the exploding gas battery of Ludwig Mond and Charles Langer (1889), as well as the carbon/air battery of W.W. Jacques (1890) proved to be operable. In Germany, Werner von Siemens was dealing with the electrochemical process called “cold burning” (hydrogen-oxygen cells), which he wanted to use mainly for the energy supply of submarines. However, the design of an efficient, high current density device only became possible when the laws of the kinetics of electrode processes have been revealed, the research of catalysts began to boom and appropriate electrolytes were constructed.

 

Rough going for technology transfer…

Launching Apollo-11
source: http://history.nasa.gov/

The early story ends with the research of Francis Thomas Bacon (1904-1992), which started in the 1930’s and opened the way for the modern development. Bacon constructed the firs alkaline fuel cell, which served on the Apollo spacecraft after 25 years of developing. In 1959, Bacon presented a 5 kW device and in the same year Harry Karl Ihrig a 20 horsepower fuel-cell driven tractor. Certainly, the different types of fuel cells have their own stories. Phosphorous acid was for long ignored because it does not conduct electricity so well as sulfuric acid. In 1961, G.V. Elmor and H.A. Tanner realized that phosphorous acid became a satisfactory conductor at a higher temperature, moreover, as opposed to sulfuric acid, it was not reduced. The first 5kW fuel cell with phosphorous acid had been prepared by 1965 for the American army, and since then the development has been unbroken. Today 50-100 kW fuel cells are used as energy sources of buses, just as their more powerful versions in the lighting and heating of buildings.

The history of solid oxide fuel cells dates back to the Nernst lapms. The work of E. Baur and H. Preis in 1930, then of H.H. Möbius, and the persistence of other researchers allowed that in 2000 a 200 kW power plant, consisting of 1152 fuel cells of the Siemens Westinghouse provides the electric supply of 200 buildings. The history of carbonate smelt cells goes parallel with the solid oxide cells; the first reliable prototypes appeared in the middle of the 1960’s. Nowadays power stations of 2 MW are operating, however, plans of 100 MW power stations are also ready. At each cell type the continuously developed new materials have always played a big role, however, the construction of polymer-electrolyte membranes was really a milestone, and a great example to demonstrate that a new material or idea can lead to a paradigm shift in some field. Polymer-electrolyte cells have been developed for spacecrafts, and only later was the technology applied for “terrestrial” use, in power plants and cars.

By the end of the 60’s, the fundamental types of fuel cell batteries had been ready to conquer the world. The traditional fuel cell elements had already been involved in foreign and Hungarian text books, however, in the 60’s modern cell types were described as well. From that on, a series of special books were published in this topic. After the Second World War, an exceptional financial support was received by the research institutes of NASA. The major aim of the Americans was to maintain and enhance their technical dominance over the USSR. Shooting the first satellite in history (Sputnik) in 1957 motivated the technological development. The most spectacular scene of the competition was space research with the aim of conquering the space. Fuel cells played an important role in the Gemini program (proton exchange membrane cells) and the Apollo program (alkaline electrolyte cells). Even those early types of fuel cells had several benefits for space flights:

• They contained no moving spare parts
• Their operation was reliable and stable
• Their operation was not influenced by gravity (this is only true for solid electrolyte types), temperature changes and cosmic radiation
• Their fuel (usually hydrogen and oxygen) was anyway part of the load.