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ALTERNATE FUEL CELLS FOR AUTOMOBILES

ABSTRACT
Today, millions of people depend on the automobile as their main source of transportation. Automobiles are the most efficient and convenient way to travel compared to walking or running. Unfortunately, most of the automobiles use fossil fuels such as oil. After the internal combustion engine consumes the gasoline, it releases carbon monoxide, nitrogen oxides, hydrogen carbons, and carbon dioxide. These chemicals cause air pollution, acid rain, and the build up of greenhouse gases in the atmosphere. This results in the destruction of our precious ozone layer. In addition to these disastrous effects to the environment, gasoline is a finite energy source. Therefore, another efficient and cheap energy source needs to be found quickly. Ideally, this energy source should be unlimited in its supply and friendly to the environment. Many alternatives have been considered. For example, researchers have attempted to power cars by the use of batteries and solar power. However, since batteries operate on a stored amount of energy, it has a limited range typically around 100 miles. The batteries are also very large since it consumes over 17 times as much space and 45 times as much weight as gasoline tanks. Solar powered cars are limited to its use on sunny days. On cloudy days and at night, the car operates on batteries. Therefore, solar powered cars have a driving range of approximately 135 miles. As a result, the best alternative to gasoline is the fuel cell. Fuel cell systems produce no polluting emissions and they contain no moving parts. Fuel cells are also 3 times more efficient than the internal combustion engine. Unlike gasoline used by the internal combustion engine, most fuel cells utilize hydrogen, a renewable resource. The use of fuel cells will decrease our dependence on the finite amount of fossil fuels. It will also spur economic growth of a country.

Principles
What makes up a fuel cell?
Hydrogen A thin and flat cell made up of two electrodes (anode and cathode) separated by a plastic sheet called a membrane .The cathode and anode are formed by an electrochemically active catalyst (link catalyst to the glossary) layer, typically platinum. Oxygen External circuit

So how does a fuel cell work?


First, the hydrogen is exposed to the anode. The anode then draws the electron from the hydrogen leaving a proton (H + ). On the opposite side of the cell, the cathode absorbs oxygen from the air. This produces a potential and causes the electron to move through an external circuit. This creates a current through the circuit which powers the electricmotor. As a result, the oxygen receives two electrons and becomes negatively charged (O 2 ). Since, there are negatively charged oxygen ions on one side of the membrane and positively charged protons (H + ) on the other side, the protons diffuse across the membrane to the cathode. Therefore, the bonding of the oxygen ion and the proton (H + ) form water. This device is called a Proton Exchange Membrane fuel cell, or PEM, because the protons (H + ions) diffuse across the membrane.

Cathode Reaction: O2 +4H++4e>2H20 Anode Reaction: H2>2H++2e The advantage of using a Protonexchange membrane fuel cell is that they have an operating range of 1 atmosphere to 8 atmospheres of pressure. PEM cells work best lower temperatures since they cannot tolerant temperature increases. The fuel cells have a high power density and flexible operation. Also, automobiles with the hydrogen fuel cells have a higher efficiency at partial loads compared with the gasoline engine.

What makes up a fuel cell engine?


Fuel cell delivery Air delivery Fuel delivery Control system Electrical system Control system Electrical drive To make a fuel cell system, several single cells must be assembled in series or parallel to form a stack of the desired current, voltage, and power. These stacks are constructed with humidifiers, pumps, and gas filters to form a fuel cell engine. An air compressor is needed to compress the air while the humidifier is used to keep the PEM membrane moist since it conducts the protons in the electrolyte only through an aqueous environment. By keeping the membrane hydrated, this allows the fuel cell to operate properly

FUEL CELL POWERED CAR

Problems
Despite the high efficiency of energy that fuel cells produce, some of the energy is lost due to the overpotential of the anodic and cathodic reactions. This is simply the voltage needed to overcome the potential barrier of the oxygen and hydrogen electrode reactions.

Also, efficiency is lost by internal cell resistance. This means that a steep voltage drop at high current density occurs in the cell because of inadequate mass transfer of the reacting species at the electrodes. Currently, fuel cell development shows that a current density of 0.81.2 A/cm 2 is possible from a single cell within a range of 0.550.75 V. However, the current density needs to be increased in order to make the hydrogen fuel cell more practical for an automobile.

Another problem is that the water management in the cell is difficult to control. The PEM fuel cell requires an aqueous membrane to operate efficiently. The fuel cells cannot be operated at high temperatures because the water inside the cell boils at 100 o C. As a result, if the cell operates on a hot or sunny day, this will cause the water inside to boil and evaporate. This will result in a dry membrane which will eventually lose its conductivity. Therefore, a humidifier is used to help keep the membrane in an aqueous environment. However, humidifiers add addition mass and consume power from the fuel cell. In addition, another limitation of the PEM fuel cell is that the Pt anode electro catalysts are extremely CO intolerant. From the cathode and anode reactions, traces of CO in reformed gases cannot be avoided. The CO poisoning is a result of the strong competitive chemisorption of CO to displace H2 from the Pt surface. Since the chemisorption of CO is exothermic, it weakens considerably with temperature and efforts to develop higher temperature PEM fuel cells are currently being designed. Finally, a major limitation of the cell is the onboard hydrogen storage. Hydrogen can be stored in a rechargeable metal hydride or in a hydride compound that releases hydrogen when reacted with water. Physically, hydrogen can be stored as compressed gas, cryogenically cooled liquid, or through the absorption of a surface. Despite these methods, storing enough hydrogen to power a car requires a large tank. With the current technology, the compressed hydrogen tank size required to contain 6.8 kg hydrogen for a 1500 kg vehicle with a driving range of 560 km is 340 L at 25 MPa. A typical gasoline tank for such a vehicle is 70 L. Thus, the challenge today is to discover a way to store enough compressed hydrogen in the vehicle without consuming too much space. This is the major obstacle impeding the progress of hydrogen fuel cell automobiles becoming a commercial product, therefore, we shall investigate this problem more in depth.

Current Hydrogen Storage/ Production Methods


As the race continues for creating a practical hydrogen fuel cell car, many different methods of storing or producing the elemental hydrogen required for the fuel cell to function. Some of these methods are presently being used in prototype vehicles, while others are still in the lab. The major methods that are being used by auto companies are methanol reformation and gasoline reformation. The methods of gasoline and methanol reformation are those currently being used in the prototype fuel cell cars. For the methanol reformation hydrogen is directly injected into the cells. There is a tank that holds the methanol, just like a gasoline tank on a conventional automobile. The methanol and water vaporize, forming hydrogen, carbon monoxide, and carbon dioxide. This takes place at near 280 degrees Celsius. After the carbon monoxide (which is in amounts of 1020 PPM) is catalyticaly oxidized, the gas is sent to the positive pole on the fuel cell. Here there is a special foil covered with a platinum catalyst and an electrode. When oxygen from the atmosphere arrives at the negative pole, hydrogen gas is converted to protons and electrons. The foil is permeable only for protons, so an electrical voltage is set up which can drive the electric motor.

Cutting Edge Research


Much of the technology that automobile companies are now using in fuel cell cars involve getting the hydrogen from another source, namely methanol or gasoline, but research is being done so that elemental hydrogen may be stored by itself. Work is also being done to combat the hydrogen storage problem indirectly with the usage of acidic electrolytes to increase the temperature at which the cells run at, and increasing the productivity of the hydrogen stored. This would mean less would need to be stored. The methods of direct storage that appear to be the most promising are those of glass micro spheres, carbon nanotubes, and graphite

Nanofibers : Nonvolatile Acidic Electrolytes


A major limitation of the PEM fuel cell is that the Pt anode electro catalysts are

extremely CO intolerant. Traces of carbon monoxide of 5 to 10 ppm cannot be avoided. To solve this problem, the reactions inside the fuel cell need to operate at temperatures above 100 o C.

However, the proton exchange membrane fuel cells cannot operate at high temperatures around 100 o C because of the evaporation of water in the membrane. To enhance the proton conductivity of ionexchange membrane at higher temperatures, researchers at the University of Iowa are using a Nafion memberane and "impregnating" it with some acidic solid. This will make a low volatile solution that would provide a high concentration of protons in the membrane pores. As a result, the nonvolatile acid will provide 3 functions inside the fuel cells. The nonvolatile acid will act as a Bronsted base solvating the proton of the stronger sulfonic acid. This creates the ion network clusters for conduction. As a result, this is the same way that a conventional protonexchange membrane works without its volatility problem. (Protonation of the Bronsted base (B) is represented by the following reaction: B + H + B H +) Scientists found that at different pressures and temperatures, the Nafion membrane impregnated with the nonvolatile acid had a dramatically higher density than conventional PEM fuel cells. For example, at 110 o C the fuel cell provided a power density of approximately 465 mW/cm 2 at 0.5 V. Its peak power was at 475 mW/cm 2 at 0.4 V. At a voltage of 0.2 V, the density of the Nafion with the nonvolatile acid had a current density of 1700 mA/cm 2 while the conventional membrane at 0.2 V produced a current density of only 200 mA/cm 2 . With the saturated Nafion membrane, a power density of 450 mW/cm 2 was obtained at 120 o C . Therefore, these results show that by soaking a perfluorosulfonic acid membrane such as Nafion with a lowvolatility acidic solution, this will allow fuel cell operation with a larger storage of hydrogen at higher temperatures. The role of the supported acid is to provide higher concentrations of protons in the membrane pores by undergoing protontransfer reactions. Even though these preliminary results show a dramatic improvement in output at higher temperatures, numerous other molten and solid acid solutions need to be tested.

Glass Micro spheres


Glass micro spheres are glass bubbles ranging in size from 25 to 500 microns in diameter,

with a thickness of about 1 micron. When the spheres are heated to temperatures of 200 degrees to 400 degrees Celsius, the glass becomes very permeable, allowing them to be filled with hydrogen gas. When the temperature is lowered, the spheres trap the hydrogen inside. When reheated, the hydrogen can escape for use. This process can store hydrogen well, but it has not yet been implemented for use with fuel cells, let alone automobiles.

Carbon Nanotubes
Carbon nanotubes are also a new method for the storage of hydrogen. One way carbon can arrange itself is in a sheet pattern like a honeycomb. This is the graphite form of carbon. The sheets are not bound tightly together, but if they are wrapped on top of each other, a very strong carbon nanotube is formed. Carbon nanotubes were discovered by Terry Baker, professor of chemistry at Northeastern University, while Terry was doing research at the Atomic Energy Authority in Harwell, England. The carbon was a waste product of catalytic reactions. As a catalytic metal reaction particle. proceeds Different platelets metals of of precipitated carbon stack below and above the

course, produce different configurations of the platelets. The carbon may stack like crackers, some may stack slanted end to end resembling a herribone, and some may stack in a bent formation creating tubes. A consistent property of the nano fibers is that the distance between each platelet is identical.

Another possibility involves charging the carbon with electrons. When this is done the hydrogen molecules squeeze between the platelets layers. This squeezing further decreases the vibrational activity hydrogen molecules which allows for further compression. The following general process is followed to allow hydrogen to be stored in the carbon: The nanotubes are first washed in acid to remove any metal impurities, they are then heated to 900 degrees C and put under a vacuum to remove any gases that may be slits on the nanofibers. Hydrogen is then pumped into the system at a pressure of 120 atm. The hydrogen can then be released by gradually reducing the pressure. Note a pressure of 40 atm must be applied to keep the hydrogen in place. The pressure where the hydrogen gas will cease to be released from the carbon tubes has also yet to be determined.2

Graphite Nanofibers
Another approach utilizes graphite nanofibers which hydrogenpowered cars could travel up to 8000 kilometres on a single tank. Graphite nanofibers can store up to three times their own weight in hydrogen under pressure at room temperature. Researchers at the Northeastern University in Boston claim that their method can store ten times more hydrogen than the current storage media. The graphite nanofibers work by using fuel cells combined with hydrogen and oxygen to produce an electric current. The graphite nanofibers are packed closely together.

They consist of stacks of graphite platelets and vary from 5 to 100 millimetres in length and from 5 to 100 nanometres in diameter. As a result, 6.2 litres of hydrogen per gram of graphite can be achieved by covering the surface of the graphite crystal in a single layer of hydrogen molecules. The high storage capacity is due to several layers of hydrogen molecules condensing inside the pores between the platelets. The spacing between the graphite layers is 0.34 nanometres while the hydrogen molecules have a diameter of 0.26 nanometres. Multiples layers of hydrogen could be squeezed into the gap if the molecules were interacting strongly with the electrons in the graphite. When the hydrogen is absorbed by the graphite, they lose a lot of rotational energy and shrink to an effective radius of 0.064 nanometres. Scientists predict that they could probably produce five layers of hydrogen through one graphite slit (Hill 20). This will allow a dramatic increase in hydrogen storage.

To pump the nanofibers with hydrogen, the nanofibers must be washed with acid to remove metal impurities from the catalyst particles. Then, they are heated to over 900 o C and placed inside a vacuum to remove any gases in the slits. After this process, hydrogen is pumped into the slits at a pressure of 120 atmospheres which takes about 4 to 24 hours for the nanofibers to be filled with hydrogen. Inside the fuel cells, the pressure must be maintained at 40 atmospheres to keep the hydrogen from escaping. The nanofibers can be refilled to the same capacity to at least 4 to 5 times. Because of the narrow slit, this stops oxygen and other larger molecules from squeezing inside. As a result, this minimizes the chance of an explosive reaction. Graphite is not expensive to produce since it will cost less than $1 per kilogram. Nanofibers are continuing to be researched as an alternative method to store hydrogen.