Sir William Robert Grove developed two electrochemical cells (batteries): the first cell consisted of zinc in dilute sulfuric acid and platinum in concentrated nitric acid, separated by a porous pot, that was practically used for the early American telegraph and the second cell, a “gas voltaic battery” was the forerunner of modern fuel cells. Thus, Grove is known as “Father of the Fuel Cell”.
William Grove was born in Swansea, Wales in 1811. He was educated by private tutors and then at Brasenose College, Oxford, graduating B.A. in 1832. He also studied law at Lincoln’s Inn.
Grove’s scientific career
His career in Science began in the late 1830s when he designed a voltaic battery and described first to the annual meeting of the British Association for the Advancement of Science in 1839. The “Grove Battery” became widely known and used, but it is now thought this achievement was surpassed by his entirely new concept of a -gaseous’ voltaic battery , a pioneer fuel cell , on which he was concurrently working.
His first cell consisted of zinc in dilute sulfuric acid and platinum in concentrated nitric acid, separated by a porous pot (Grove Battery). The cell was able to generate about 12 amps of current at about 1.8 volts. This cell had nearly double the voltage of the first Daniell cell. Grove’s nitric acid cell was the favorite battery of the early American telegraph (1840-1860), because it offered strong current output. As telegraph traffic increased, it was found that the Grove cell discharged poisonous nitric dioxide gas.
Large telegraph offices were filled with gas from rows of hissing Grove batteries. As telegraphs became more complex, the need for constant voltage became critical and the Grove device was necessarily limited (as the cell discharged, nitric acid was depleted and voltage was reduced). By the time of the American Civil War, Grove’s battery was replaced by the Daniell battery.
This is a fragment of a book giving description of the Grove’s battery:
The Grove Battery. The most intense and powerful voltaic combination that has yet been discovered is that of Grove. For many years it was exclusively used for telegraphic purposes in this country, and is still employed in that capacity to a considerable extent. Its component parts are shown in Fig. 5, in which A represents a glass jar or tumbler, about 3 inches in diameter and 4 1/2 inches high.
A thick cylinder of zinc, B, of a size nearly sufficient to fill the tumbler, is placed within it, and is furnished with a projecting arm, to which is attached the positive plate of the next element. The porous cup, C, is placed within the zinc. A thin strip of platina, D, about 2 1/2 inches long and half an inch in width, is soldered to the end of the zinc arm projecting from the adjacent cell, and reaches nearly to the bottom of the porous cup.
Setting up a Grove Battery. It is necessary that the zinc should first be thoroughly amalgamated. The ordinary zinc of commerce contains particles of lead, iron, and other impurities, which, when the plate is immersed in dilute acid, form as it were small batteries upon the surface, which eat away numerous cavities in the zinc without producing any useful effect.
This is prevented by the above process of amalgamation, which is usually performed by immersing the zincs in a vessel containing dilute muriatic or sulphuric acid, and then plunging them in a bath of metallic mercury. After remaining in this for a minute or two they are taken out and placed in a vat of clean water, where the superfluous mercury is allowed to drain off. The mercury dissolves a little of the zinc, which flows over and covers the impurities, and prevents the acid solution from coming in contact with them.
In putting the Grove battery together, first place the glass tumblers in position and fill them about half full of a solution composed of one part of sulphuric acid and twenty to thirty parts water, by measure, thoroughly mixed. Then place the amalgamated zincs in the tumblers, with the arms turned at right angles to the line of cells. Fill the porous cups nearly full of strong nitric acid and place them within the zincs, then turn the zincs around so as to immerse the platina strips in thenitric acid of the adjoining cell, throughout the whole series, as shown at T, in Fig. 5.
The strength of the dilute sulphuric acid solution in this battery should be varied in proportion to the number of wires worked from it. The less the number of the latter the weaker the solution may be made.
When in continuous service a Grove battery ought to be taken apart every night, and the nitric acid from the porous cups emptied into a vessel and kept closed until morning. The zincs should be removed and placed inverted in a trough of water, acidulated with sulphuric acid, and in the morning rubbed with a brush, and the mercury diffused evenly over their surfaces.
To every ten parts of the nitric acid taken from the battery add one part of fresh acid every morning. By this means a steady and uniform current will be maintained when the battery is in action. The dilute sulphuric acid requires renewal about twice a week. In handling this battery great care is required not to injure the connection between the zinc and the platina. A set of Grove zincs, in continuous service, will require renewal about once in three months.
The first Fuel Cell
His second cell, a “gas voltaic battery” was the forerunner of modern fuel cells. William Grove produced the first fuel cell in 1839 over 150 years ago. He based his experiment on the fact that sending an electric current through water splits the water into its component parts of hydrogen and oxygen.
So, Grove tried reversing the reaction – combining hydrogen and oxygen to produce electricity and water. This is the basis of a simple fuel cell. The term “fuel cell” was coined later in 1889 by Ludwig Mond and Charles Langer, who attempted to build the first practical device using air and industrial coal gas.
Fuel cells got their start when William Grove immersed two platinum strips surrounded by closed tubes containing hydrogen and oxygen in an acidic electrolyte (see Grove’s Device below).William Grove’s originalfuel cell used dilute sulfuric acid because the reaction depends upon the pH when using an aqueous electrolyte.
This first fuel cell became the prototype for the Phosphoric Acid Fuel Cell (PAFC), which has had a longer development period than the otherfuel cell technologies. Unfortunately, he was hampered by the inconsistency of cell performance (a common feature of cells today), but realized the importance of the three phase contact (gas, electrolyte and platinum) to energy generation.
He spent most of his time searching for an electrolyte that would produce a more constant current. He found several electrolytes which produced current, but still struggled with consistent results. He also noted the potential of the energy production method commercially if hydrogen could replace coal and wood as energy sources.
Grove’s Device: Oxygen and hydrogen in the tubes over the lower resevoirs react in sulfuric acid solution to form water. That is the energy producing chemical reaction. The electrons produced electrolyze water to oxygen and hydrogen in the upper tube that was actually used as a voltmeter.
This scheme was published by Grove in one of the first accounts of an operating fuel cell in Philos. Mag., Ser. 3, 1839, 14, 127. Grove proved that his fuel cells worked, but as he had no entrepreneurial inclinations, and there was no practical use for them at that time anyway, the invention slumbered for more than 130 years.
The figure shown left appears on page 272 of the Philosophical Magazine and Journal of Science, 1843, with William Grove’s letter “On the Gas Voltaic Battery.” Grove undertook the series of thirty experiments described in this letter when, “after my original publication I received a letter from Dr. Schoenbein [Christian F. Schonbein (1799-1868)] … [who] there expresses an opinion, that in the gas battery oxygen does not immediately contribute to the production of current, but that it is produced by the combination of hydrogen with water.” One of the gas battery configurations used in Grove’s experiments is seen here.
“In figure 6, a battery of five cells … is represented as when charged [filled] with oxygen and hydrogen, and having been for some time connected with the voltmeter (figure 7), the tubes of which are of the same size as those of the battery.” These are labeled “o” and “h” in the drawing.
Grove wrote, “ten cells charged to a given mark on the tube with dilute sulphuric acid … oxygen and hydrogen, were arranged in circuit with an interposed voltameter … and allowed to remain so for thirty-six hours. At the end of that time 2.1 cubic inches of mixed gas were evolved in the voltameter; the liquid had risen in each of the hydrogen tubes of the battery to the extent of 1.5 cubic inch, and in the oxygen tubes 0.7 cubic inch, equalling [sic] altogether 2.2 cubic inches; there was therefore 0.1 cubic inch more of hydrogen absorbed in the battery tubes than was evolved in the voltameter. This experiment was repeated several times with the same general result.”
In the course of these experiments, Grove provided strong evidence that producing current required both hydrogen and oxygen. However, he also raised questions about the production of heat and “novel gaseous and liquid products”-questions that he could not answer with the equipment and theory available to him. These questions became puzzles for later researchers to solve.
An older friend and co-enthusiast for research in electricity, John P. Gassiot (1797-1877), was of considerable influence and help in encouraging Grove to pursue a scientific career in the early 1840s when the conflict between the desire for research and the pressure to devote himself to the legal profession was at a height. Elected FRS in 1840, Grove played a vigorous part in reform of the administration of the Royal Society in the following years. At the same period (1840-1847) Grove became Professor of Experimental Philosophy at the London Institution in the City of London.
There he lectured usually during the months of November and December, on a variety of scientific subjects. He used his platinum-zinc batteries to produce electric light for one of his lectures. His most significant lectures were a course of six given in 1843 on “The correlation of Physical Forces’, concerning his early ideas of the conservation of energy.
He published the subject as a book in 1846 which by 1874 achieved the sixth edition. In this book he enunciated the principle of conservation of energy a year before the German physicist Hermann von Helmholtz did so in his famous paper Ãœber die Erhaltung der Kraft (“On the Conservation of Force”).
Grove first offered proof of the thermal dissociation of atoms within a molecule. He showed that steam in contact with a strongly heated platinum wire is decomposed into hydrogen and oxygen in a reversible reaction. Grove was the first to show that electrolysis, with a high-tension current, can take place through thin glass.
He took a considerable interest in photographic science during the 1840s. In 1841 he experimented (with some collaboration from J. P. Gassiot) at the London Institution with daguerreotype plates for photomechanical printing. A paper on this -voltaic process for etching daguerreotype plates’ was read at a meeting of the London Electrical Society on 17 August 1841 and the prints he displayed there ought to, he suggested, have been inscribed -drawn by Light and engraved by Electricity’. Grove’s belief in the future influence of the new technology of photography was expressed in a lecture he delivered at the London Institution on 19 January 1842:
“It would be vain to attempt specifically to predict what may be the effect of photography on future generations. A process by which the most transient actions are rendered permanent, by which facts write their own annals in a language that can never be obsolete, forming documents which prove themselves, , must interweave itself not only with science but with history and legislature. It provided an example in which the researcher not only gives to Man new physical knowledge, but works an indelible change in his moral destinies.”
Grove went to the annual meeting of the British Association for the Advancement of Science at York in 1844 and described experiments using nitric acid to obtain direct-positive calotype prints. While at York he had his portrait (shown left) taken by Robert Adamson and D.O. Hill.
(reproduced from R. D. Wood (1975), the original being at the Scottish National Portrait Gallery)
Grove’s career as a lawyer
Grove followed two careers: as a scientist and as a lawyer in the courts of Common Law. He became a Barrister of Lincoln’s Inn in 1835, was made a Queen’s Counsel in 1853 and a Judge of the Court of Common Pleas in 1871. He also served in the High Court of Justice. Grove’s knowledge of science made him an ideal choice as a lawyer in technical lawsuits and it seems likely that a large part of his legal practice lay in patent cases.
He served as a lawyer for the defence in the case of Beard vs. Egerton that was important in the history of the daguerreotype patent in England in the courts from 1845 to 1849. Grove became famous, or perhaps infamous, as the defender of Dr. William Palmer, the “Rugeley poisoner.” Ill health interrupted his law career, and he turned to science. After retirement from the bench in 1887, he resumed his scientific studies.
William Grove married when he was twenty five and had six children. Grove was knighted in 1872.
Fuel cell history
Researchers have been working on the basic scheme described above for over 150 years and provided many variations on fuel, electrodes and electrolytes. Sir Humphrey Davy created in 1802 a simple fuel cell that allowed him to give himself a feeble electric shock. However, this result was not well documented. The basic principle of the Fuel Cell technology was already invented or discovered in 1839. The German/Swiss Christian Friedrich Schonbein published his article about the hydrogen-oxygen Fuel Cell in the “Philosophical Magazine” in January 1839. Around that time the English Sir William Grove was working on the series or parallel connections of his powerful platinum-zinc battery.
In the post-scriptum to his article published also in the “Philosophical Magazine”, February 1839, Sir Grove indicated the possibility of the hydrogen-oxygen reaction to generate electricity. In 1842 Sir Grove presented the Fuel Cell in all its details. Later fuel cells such as those constructed by William White Jaques (who incidentally coined the term fuel cell) substituted phosphoric acid H3PO4 in the electrolyte bath.
Significant fuel cell research was done in Germany during the 1920′s that laid the ground work for subsequent development of carbonate cycle and solid oxide fuel cells. Perhaps the most important fuel cell research of the 20th century was conducted by Dr. Francis T. Bacon (he was a direct descendent of the Francis Bacon) who developed – (drum rolls) the Bacon Cell. Dr. Bacon substituted an acid electrolyte with an alkali electrolyte (potassium hydroxide – KOH). KOH performs as well as acid as an electrolyte and is not as corrosive on the electrodes.
The Bacon design was chosen by NASA for the power supply for the Apollo mission and the STS shuttle orbiters. Serious interest in the fuel cell as a practical generator did not begin until the 1960s, when they were chosen as the fuel of choice for the U.S. space program over nuclear power, considered too risky, and solar energy, considered too expensive. Fuel cells furnished power for the Gemini and Apollo spacecrafts, and provide electricity and water for the space shuttle.