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Tien Nguyen Dr. John Haan Chemistry 395 May 11, 2012 Introduction Electricity was once seen as the future; however, it will soon be a thing of the past. Electricity has been utilized in so many different ways that it has become an irreplaceable energy source. Its major downside is that electricity is generated through natural products such as coal and natural gas. However, these natural resources are not a renewable source and soon these limited natural resources will become depleted. Thus, an alternative energy source will be needed once we can no longer use natural products to generate electricity. The answer to this problem is fuel cell. Fuel cells are an alternative power source to electricity and it is most likely in the future that fuel cell will replace electricity as the major power source. Like electricity, fuel cells have had a very long history. The first person who was credited for discovering the basic principle behind fuel cells was William Grove in 1839. Grove, a lawyer and scientist, was able to split water into hydrogen and oxygen by passing a current through it. The reaction is often compared to a combustion reaction. For a combustion to work, there needs to be oxygen gas. So in a combustion reaction, a molecule is burned in O2 gas. The overall reaction of a hydrogen fuel cell is: 2H2 + O2 H2O A general combustion reaction releases heat because the reaction is very exothermic. (1) However,

a hydrogen fuel reaction is not a combustion reaction so instead of releasing heat energy, it releases electrical energy (1). Fuel cells were given its name by Charles Langer and Ludwig

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Mond. However, it was Francis Bacon was the first person to develop a fuel device that was fully functional (2). However, it was not until NASA starting funding for research in fuel cells did people become more interested in this topic. Today, fuel cells are a major power source to the space program and fuel cells have been used in electronic devices such as cell phones, laptops, and even cars. One of the benefits of fuel cells in general is that it has low-to-zero emissions. If the fuel used is pure hydrogen, than there will be no emissions. Hydrocarbons and natural gas have very low emissions when comparing to power plants. Another benefit of fuel cells are that its efficiency is very high. When compared to combustion systems, its efficiency is off the roof because there is no heat loss in the reaction so the efficiency of fuel to electricity can go over 85 percent. Fuel cells are very reliable because it can serve as the backup power source if there is a power outage. The different types of fuel used increases the flexibility of the fuel cell. As long as there is a hydrogen source, the fuel cell would work. Fuel cells are very durable and they can be placed anywhere. If more power is needed, fuel cells can be combined to supply the needed power. Also fuel cells are lightweight and long lasting. It is very light compared to batteries and it does not need to be recharge as long as there is fuel available (3). There are many fuel cells that are commercially available. One of the most prominent and popular fuel cells is the hydrogen fuel cell. The fuel for hydrogen fuel cells is any compound with hydrogen. The hydrogen source combined with the oxygen gas from the air produces water and other byproducts depending on the hydrogen source. Like electricity, it mainly uses natural gas and coal as a source of hydrogen. Natural gas is a good source of hydrogen because it comprises of hydrocarbons. There are other hydrogen source like biomass

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and hydro wind solar. These clean hydrogen fuel source will eventually replace the natural gas and coal as the main source of hydrogen. The drawback of the hydrogen-oxygen fuel cell is that consumers are afraid to use products that are engineered using a hydrogen fuel cell as the major power source. Two types of fuel commonly used are ethanol and formic acid. A major setback of the fuel is that small portable devices such as cell phones and laptops would not be able to use hydrogen fuel cells as a source of power. Another setback for this type of fuel is that the overall experiment is very slow. A third setback for the fuel is that under acidic conditions, the catalyst has to be a noble metal such as palladium or platinum because the acid will deteriorate in acid. Also, the catalyst is bound for poisoning caused by the acid. The fourth setback is that the membrane does not prevent the fuel from crossing over. Thus, this can be very dangerous for non-noble metal catalyst. The last major setback these types of fuel is that methanol is very toxic and the environment of the fuel cells are not very ideal due to its corrosiveness (4). Another popular fuel cell that is widely use is the direct liquid fuel cell. These fuel cells are used in portable electronics such as cell phones and laptop batteries. Methanol, ethanol, and formic acid are three types of fuel that are mainly used for the direct liquid fuel cell. The overall reaction is that the fuel and the oxygen from the surrounding area combine to produce carbon dioxide and water. What is interesting about the fuel cell is that the carbon dioxide form can be turn back into fuel through the partial hydrogenation. Thus, the direct liquid fuel cell is much cleaner than the hydrogen fuel cell (5). Another type of fuel cell is the acid electrolyte fuel cell. Today it is still very popular. Like a battery, the fuel cell has an anode and a cathode. At the anode, hydrogen gas loses electrons and is oxidized to H+ ions according to the following equation

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2H2 4H+ + 4e-

(2)

This reaction is responsible for the electrical energy that is produced in the fuel cells. At the cathode, oxygen gas gains the electrons and is reduce according to the following equation O2 + 4e- + 4H+ 2H2O (3)

This is the overall equation of a fuel reaction. Oxygen from the air is combined with hydrogen ions from a hydrogen source. In an acid electrolyte fuel cell, the hydrogen source is acid. Thus, sulfuric acid is a popular fuel for this type of fuel cell. Sulfuric acid is a strong acid and so there is a high concentration of H+ ions available because it completely dissociates. Thus a weak acid such as hydrofluoric acid would not be a great fuel because weak acids do not completely dissociates and so there is a low concentration (1). Another popular fuel cell is the alkaline electrolyte fuel cell. This type of fuel cell is the complete opposite of the acid electrolyte fuel cell. However, both fuel cells have the same overall reaction with water being produce at the end of the reaction. The acid electrolyte fuel cell has an available hydrogen ion supply while the alkaline electrolyte fuel cell has a bountiful supply of hydroxyl ions. At the anode, the overall reaction is: 2H2+ 4OH- 4H2O + 4e(4)

The equation shows that the hydroxide loses the electrons and so it becomes oxidized. At the cathode, the overall reaction is O2+ 4e- +2H2O 4 OH(5)

Thus the oxygen gas from the air gains electrons and so it becomes reduced. An electrical current is needed so that reaction can occur. One can see that water use is used up at the cathode; however, the rate of water being produced is twice as much as it is lost so water is still produced in the overall reaction. Thus, a good fuel for an alkaline electrolyte fuel cell is any fuel

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that gives OH- ions in the solution. Typical fuels used are strong bases because they completely dissociate, and so there is a high concentration of hydroxide ions. Thus, salts such as NaOH and KOH are good for making the fuels for this type of fuel cell because these salts will give a high concentration of hydroxide ions (1). The fuel cell mainly studied in Dr. Haans lab is called the alkaline direct liquid fuel cell. Unlike the direct liquid fuel cell and the hydrogen fuel cell which has hydrogen ions passing through the polymer electrolyte membrane, the alkaline direct liquid fuel cell passes hydroxide ions through the membrane. Instead of using hydrocarbons or acid as the fuel, bases are used. The advantage of using the alkaline direct liquid fuel cell is that the catalyst that contains transition metals does not corrode or deteriorate in the fuel compared to its counterparts. This type of fuel cell makes it possible to test out different types of metals besides palladium and platinum so we would not have to rely on these expensive metals. Compared to the hydrogenoxygen fuel cell, it has a faster oxidation rate for small organic molecule fuel such as methanol. Also a major advantage of the alkaline fuel cell is that the membrane it uses, which is the anion exchange membrane, prevents the crossing over of the fuel through the membrane (4). In the lab, a half cell is used to determine the efficiency of a fuel cell. By knowing the oxidation rate of the half cell, we can determine the efficiency of the fuel cell. If we are able to increase the oxidation rate, than it would also increase the efficiency of the fuel cell. Three types of electrode are used in a half cell. One of the three electrodes is named the reference electrode, another is called the working electrode, and the third electrode is called the counter electrode. The electrode use in my experiments is called the Hg/HgO reference electrode. The working electrode is where the reaction takes place. A catalyst is applied to the surface of the electrode and binder such as Nafion is applied if the catalyst does not stick to the surface. In my

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experiments, I use a rotating electrode so that it makes controls the effect of diffusion so that it does not affect the experiment. The counter electrode is responsible for the flow of the electrons. Without the counter electrode, the process would not be able to be performed. The reference electrode is responsible for the control of the current. A fixed current is applied and the reference electrode makes sure the current is at the applied fixed point. (6) There are four methods one can perform to test out the efficiency of a fuel cell. Those methods are potentiometry, electrogravimetry, amperometry, and voltammetry. In order for potentiometry to work, there has to be zero flow of current. By having zero flow of current, the cell potential can be measure and used for chemical analysis. Electrogravimetry can only work if the potential or current is constant. It can be used to measure the mass of the material deposited at an electrode. In order to perform an amperometry, the cell potential must be constant. By having a constant cell potential, the current can be measured. Voltammetry is used to measure the current when the cell potential is changed. (6) A very popular fuel that is often used in the direct liquid fuel cell is ethanol. However, potassium formate is another fuel that is considered to be a good fuel and have been showing signs that it can be a better fuel than ethanol. Recently, a study was done on comparing the two fuels. A current test was performed on the two fuels for five hour at a stable current of 100 mA cm-2. After five hours, the ending voltage was measured to be around 280 mV in ethanol. The ending voltage for the experiment run in potassium formate was around 580 mV. The ending current in potassium formate experiment is almost twice as high as the ending current obtained in the ethanol. What is promising about this experiment was that by changing the fuel of the experiment, the efficiency of the fuel increased dramatically. (4)

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Another item needed in the fuel cell for it to be efficient is a membrane. The membrane is responsible for passing the ions over from the anode to the cathode. In a hydrogen fuel cell, a nafion polymer membrane is used. The nafion polymer membrane was developed in the 1960s. Basically, it passes the hydrogen ions from the anode to the cathode. The membrane used in

the alkaline direct liquid fuel cell is called the anion exchange membrane and it was developed by Tokuyama. Like the nafion polymer membrane, it is responsible for passing the ions from the anode to the cathode. However, it passes hydroxide ions instead of hydrogen ion. Without a membrane, a fuel cell would not be very efficient. (4) However, there are barriers that the fuel cells must cross before it can be considered efficient. Like every chemical reaction, there is an activation energy that needs to be overcome before work can be done. Thus it is necessary to consider what catalyst to use, the temperature the experiment would run at, and the area of the electrode. The best catalyst to use for fuel cells is platinum. Another catalyst that is often used is palladium. Thus, these two catalysts are useful when one wants a faster reaction. Temperature has always been a factor in many chemical reactions. Increase the temperature in a reaction and the kinetic energy of the molecules will increase. Thus the temperature of the fuel in a cell can be increase to speed up the reaction. The size and design of the electrode use is very important in overcoming the activation energy. If the area of the electrode is huge, more catalyst can be deposit on the electrode which increases the output current. (1) In fuel cells, the main catalyst used is platinum. The current price for an ounce of platinum is roughly $1521.00 (7). An alternative to this costly catalyst has been palladium. The current price of an ounce of palladium is roughly $635.61 (8). However, at this reduced cost, it

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is simply still too expensive.

By reducing the cost of the catalyst, the cost of a fuel cell would

decrease significantly and so there will be more opportunities to run more experiments. The five studied catalytic transition metals that are being researched are iron, cobalt, nickel, copper, and zinc. Unlike the expensive palladium and platinum catalyst, these metals only cost $0.05 to $40.00 an ounce. By developing a hybrid between palladium and one of these five transition metals, the cost of the catalyst will decrease significantly. Recent studies have shown some promising signs in these types of hybrid catalysts. For example, a hybrid catalyst consisting of nickel and palladium was produced. Cyclic voltammetry was performed on the hybrid catalyst in formate. Cyclic voltammetry was also performed on a control, which was just the palladium as the catalyst. After the cyclic voltammetry, the results show that the current using the hybrid catalyst was much higher than the palladium catalyst itself. When using ethanol as the fuel, the current of the hybrid catalyst was doubled of that of the control catalyst. (9) Another interesting experiment conducted by the same author was the mixing of multiple metals with palladium. One catalyst used in the experiment was called the Zinc Pd Carbon (ZnPd/C) on carbon catalyst and the other catalyst used in the experiment was Nickel Zinc Pd Carbon (NiZnPd/C). Cyclic voltammetry was measured for both catalyst in formate and the ZnPd/C catalyst had a much higher current than that of the NiZnPdC catalyst. These experiments shows very promising signs that the hybrid catalyst being synthesized would dramatically reduce the cost of working with fuel cells. (9) There is another experiment that the author also performed that shows the limitations of the hybrid catalyst. The control of the experiment was the ZnPdC. The other catalyst was a ZnPdC catalyst as well, but unlike the other catalyst which had a ratio of 1:1 of Zn to Pd, this new catalyst had a 3:1 ratio of Zn to Pd. Cyclic voltammetry was ran on both catalyst the current

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in the control was sixth time greater than that of catalyst with a higher percentage of zinc. Thus, the efficiency of the new catalyst can be said to be limited by the ratio of palladium to catalyst in the metal. (9) The previous experiments mentioned above show some signs that a new catalyst can be made by combining specific transition metals with palladium. However, the data would have been more significant if the surface area of the catalyst was used. The surface area of the catalyst would give us a better starting position. In our lab, my colleagues and I are working on synthesizing a new catalyst using iron, cobalt, and nickel. Of the three metals, I am currently working with cobalt. The new catalyst I synthesized is called Palladium and Cobalt on carbon catalyst (PdCoC). Basically this catalyst is an equal mixture of palladium and cobalt. To find the surface area of the catalyst, three methods were used. The first was running a cyclic voltammetry in 1M KOH. There has yet to be a specific method for calculating the surface area in the base so the calculated surface area is just a rough estimate. The second method used was to run a cyclic voltammetry in 1M H2SO4. The method used for calculating the surface area of the catalyst in acid can be trusted because the surface area calculated is very consistent with one another. The third method that is also used is to calculate the surface area of the catalyst using the mass method. Like the second method, it is reasonable to say the calculated surface area is consistent. The cyclic voltammetry in 1M KOH is run first because base does not cause the catalyst to deteriorate. The cyclic voltammetry in 1M H2SO4 is run last because the catalyst is not recycled and so it is fine for the catalyst to deteriorate in acid. The surface area is helpful because it can be used to adjust the actual current of the catalyst. A cyclic voltammetry and a chronoamperometry were run for the catalyst and these experiments were between the cyclic voltammetry before in 1M KOH and the cyclic voltammetry after in 1M H2SO4. The fuel used

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was 1M KOH and 1M KCOOH. The project was later modified and the cyclic voltammetry in base was removed because the surface area was not very prcised. Also the chronoamperometry was reduced from one hour to thirty minutes because the catalyst stabilizes before the time. However, the parameters of the cyclic voltammetry in acid were changed so that the surface area calculated will be more precise. The control of the experiment was just palladium as the catalyst and it was run using the same methods and the same parameters. Another experiment that we are currently working on as well is testing out catalytically activity of the transition metals we are using. Instead of running a 3:1 ratio of metal to palladium, we synthesize a catalyst that is one hundred percent cobalt. The catalyst was run using the same methods as our other project. Also, the parameters were kept. A cyclic voltammetry was run in 1M KOH. This was followed by the cyclic voltammetry in 1M KOH and 1M KCOOH. The last test in the experiment was a cyclic voltammetry in H2SO4. However, the results for this project were not very promising and it was put on hold. The goal of my experiments is to synthesize a catalyst that is cheap and efficient. Thus, if cobalt can substitute for palladium as the main catalyst, than the cost to operate a fuel cell will be really low. Also efficiency of the catalyst comes into play as well. We want a catalyst that ideally works as well as palladium or platinum. If cobalt can increase the efficiency of the fuel cell by increasing the current than it would turn into a very ideal catalyst.

Works Cited
1. Dicks, Andrew and Larminie, James. Fuel Cell Systems Explained: Second Edition. London : John Wiley & Sibs Ltd. , 2003.

Nguyen 11 2. SAE International . History of Fuel Cells. SAE International. [Online] 2012. [Cited: May 4, 2012.] http://www.sae.org/fuelcells/fuelcells-history.htm. 3. Fuel Cells. Benefits. Fuell Cells. [Online] 2012. [Cited: May 11, 2012.] http://www.fuelcells.org/fuelcells-and-hydrogen/benefits/. 4. The direct formate fuel cell with an alkaline anion exchange membrane. Bartrom, Amy and Haan, John L. 2012, Power, pp. 1-7. 5. Haan, John, [perf.]. Akaline Fuel Cells: They Sent a Man to the Moon but Not the Grocery Store...Yet. Fullerton : s.n., 2012. 6. . Spectrophotometry & Calibration Curve . Fullerton : s.n., 2012. 7. Platinum Price . Platinum Price Per Ounce. Platinum Price . [Online] May 4, 2012. [Cited: May 4, 2012.] http://platinumprice.org/platinum-price-per-ounce.html. 8. Palladium Price. Palladium Price Per Ounce. Palladium price. [Online] May 5, 2012. [Cited: May 5, 2012.] http://palladiumprice.org/palladium-price-per-ounce.html.