FuelCell Fundamentals

A fuel cell is a device that converts the chemical energy from a fuel into electricity through a chemical reaction of positively charged hydrogen ions with oxygen or another oxidizing agent. Fuel cells are different from batteries in that they require a continuous source of fuel and oxygen or air to sustain the chemical reaction, whereas in a battery the chemicals present in the battery react with each other to generate an electromotive force (emf). Fuel cells can produce electricity continuously for as long as these inputs are supplied.

The first fuel cells were invented in 1838. The first commercial use of fuel cells came more than a century later in NASA space programs to generate power for satellites and space capsules. Since then, fuel cells have been used in many other applications. Fuel cells are used for primary and backup power for commercial, industrial and residential buildings and in remote or inaccessible areas. They are also used to power fuel cell vehicles, including forklifts, automobiles, buses, boats, motorcycles and submarines.

There are many types of fuel cells, but they all consist of an anode, a cathode, and an electrolyte that allows positively charged hydrogen ions (or protons) to move between the two sides of the fuel cell. The anode and cathode contain catalysts that cause the fuel to undergo oxidation reactions that generate positively charged hydrogen ions and electrons. The hydrogen ions are drawn through the electrolyte after the reaction. At the same time, electrons are drawn from the anode to the cathode through an external circuit, producing direct current electricity. At the cathode, hydrogen ions, electrons, and oxygen react to form water. As the main difference among fuel cell types is the electrolyte, fuel cells are classified by the type of electrolyte they use and by the difference in startup time ranging from 1 second for proton exchange membrane fuel cells (PEM fuel cells, or PEMFC) to 10 minutes for solid oxide fuel cells (SOFC). Individual fuel cells produce relatively small electrical potentials, about 0.7 volts, so cells are “stacked”, or placed in series, to create sufficient voltage to meet an application’s requirements.[2] In addition to electricity, fuel cells produce water, heat and, depending on the fuel source, very small amounts of nitrogen dioxide and other emissions. The energy efficiency of a fuel cell is generally between 40–60%, or up to 85% efficient in cogeneration if waste heat is captured for use.

fuelcell

Types of fuel cells

Fuel cells come in many varieties; however, they all work in the same general manner. They are made up of three adjacent segments: the anode, the electrolyte, and the cathode. Two chemical reactions occur at the interfaces of the three different segments. The net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices, normally referred to as the load.

At the anode a catalyst oxidizes the fuel, usually hydrogen, turning the fuel into a positively charged ion and a negatively charged electron. The electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot. The freed electrons travel through a wire creating the electric current. The ions travel through the electrolyte to the cathode. Once reaching the cathode, the ions are reunited with the electrons and the two react with a third chemical, usually oxygen, to create water or carbon dioxide.

A block diagram of a fuel cell

The most important design features in a fuel cell are:

  • The electrolyte substance. The electrolyte substance usually defines the type of fuel cell.
  • The fuel that is used. The most common fuel is hydrogen.
  • The anode catalyst breaks down the fuel into electrons and ions. The anode catalyst is usually made up of very fine platinum powder.
  • The cathode catalyst turns the ions into the waste chemicals like water or carbon dioxide. The cathode catalyst is often made up of nickel but it can also be a nanomaterial-based catalyst.

A typical fuel cell produces a voltage from 0.6 V to 0.7 V at full rated load. Voltage decreases as current increases, due to several factors:

  • Activation loss
  • Ohmic loss (voltage drop due to resistance of the cell components and interconnections)
  • Mass transport loss (depletion of reactants at catalyst sites under high loads, causing rapid loss of voltage).

To deliver the desired amount of energy, the fuel cells can be combined in series to yield higher voltage, and in parallel to allow a higher current to be supplied. Such a design is called a fuel cell stack. The cell surface area can also be increased, to allow higher current from each cell. Within the stack, reactant gases must be distributed uniformly over each of the cells to maximize the power output.

Proton exchange membrane fuel cells (PEMFCs)

Main article: Proton exchange membrane fuel cell

In the archetypical hydrogen–oxide proton exchange membrane fuel cell design, a proton-conducting polymer membrane (typically nafion) contains the electrolyte solution that separates the anode and cathode sides. This was called a “solid polymer electrolyte fuel cell” (SPEFC) in the early 1970s, before the proton exchange mechanism was well-understood. (Notice that the synonyms “polymer electrolyte membrane” and “proton exchange mechanism” result in the same acronym.)

On the anode side, hydrogen diffuses to the anode catalyst where it later dissociates into protons and electrons. These protons often react with oxidants causing them to become what are commonly referred to as multi-facilitated proton membranes. The protons are conducted through the membrane to the cathode, but the electrons are forced to travel in an external circuit (supplying power) because the membrane is electrically insulating. On the cathode catalyst, oxygen molecules react with the electrons (which have traveled through the external circuit) and protons to form water.

In addition to this pure hydrogen type, there are hydrocarbon fuels for fuel cells, including diesel, methanol (see: direct-methanol fuel cells and indirect methanol fuel cells) and chemical hydrides. The waste products with these types of fuel are carbon dioxide and water. When hydrogen is used, the CO2 is released when methane from natural gas is combined with steam, in a process called steam methane reforming, to produce the hydrogen. This can take place in a different location to the fuel cell, potentially allowing the hydrogen fuel cell to be used indoors—for example, in fork lifts.

Construction of a high-temperature PEMFC: Bipolar plate as electrode with in-milled gas channel structure, fabricated from conductive composites (enhanced with graphite, carbon black, carbon fiber, and/or carbon nanotubes for more conductivity); Porous carbon papers; reactive layer, usually on the polymer membrane applied; polymer membrane.

Condensation of water produced by a PEMFC on the air channel wall. The gold wire around the cell ensures the collection of electric current.

The different components of a PEMFC are

  1. bipolar plates,
  2. electrodes,
  3. catalyst,
  4. membrane, and
  5. the necessary hardware such as current collectors and gaskets.

The materials used for different parts of the fuel cells differ by type. The bipolar plates may be made of different types of materials, such as, metal, coated metal, graphite, flexible graphite, C–C composite, carbon–polymer composites etc.[24] The membrane electrode assembly (MEA) is referred as the heart of the PEMFC and is usually made of a proton exchange membrane sandwiched between two catalyst-coated carbon papers. Platinum and/or similar type of noble metals are usually used as the catalyst for PEMFC. The electrolyte could be a polymer membrane.

Proton exchange membrane fuel cell design issues

  • Costs. In 2013, the Department of Energy estimated that 80-kW automotive fuel cell system costs of US$67 per kilowatt could be achieved, assuming volume production of 100,000 automotive units per year and US$55 per kilowatt could be achieved, assuming volume production of 500,000 units per year.[25] Many companies are working on techniques to reduce cost in a variety of ways including reducing the amount of platinum needed in each individual cell. Ballard Power Systems has experimented with a catalyst enhanced with carbon silk, which allows a 30% reduction (1 mg/cm² to 0.7 mg/cm²) in platinum usage without reduction in performance. Monash University, Melbourne uses PEDOT as a cathode. A 2011 published study[28] documented the first metal-free electrocatalyst using relatively inexpensive doped carbon nanotubes, which are less than 1% the cost of platinum and are of equal or superior performance. A recently published article demonstrated how the environmental burdens change when using carbon nanotubes as carbon substrate for platinum.[29]
  • Water and air management (in PEMFCs). In this type of fuel cell, the membrane must be hydrated, requiring water to be evaporated at precisely the same rate that it is produced. If water is evaporated too quickly, the membrane dries, resistance across it increases, and eventually it will crack, creating a gas “short circuit” where hydrogen and oxygen combine directly, generating heat that will damage the fuel cell. If the water is evaporated too slowly, the electrodes will flood, preventing the reactants from reaching the catalyst and stopping the reaction. Methods to manage water in cells are being developed like electroosmotic pumps focusing on flow control. Just as in a combustion engine, a steady ratio between the reactant and oxygen is necessary to keep the fuel cell operating efficiently.
  • Temperature management. The same temperature must be maintained throughout the cell in order to prevent destruction of the cell through thermal loading. This is particularly challenging as the 2H2 + O2 -> 2H2O reaction is highly exothermic, so a large quantity of heat is generated within the fuel cell.
  • Durability, service life, and special requirements for some type of cells. Stationary fuel cell applications typically require more than 40,000 hours of reliable operation at a temperature of −35 °C to 40 °C (−31 °F to 104 °F), while automotive fuel cells require a 5,000-hour lifespan (the equivalent of 240,000 km (150,000 mi)) under extreme temperatures. Current service life is 2,500 hours (about 75,000 miles). Automotive engines must also be able to start reliably at −30 °C (−22 °F) and have a high power-to-volume ratio (typically 2.5 kW per liter).
  • Limited carbon monoxide tolerance of some (non-PEDOT) cathodes.

Phosphoric acid fuel cell (PAFC)

Main article: Phosphoric acid fuel cell

Phosphoric acid fuel cells (PAFC) were first designed and introduced in 1961 by G. V. Elmore and H. A. Tanner. In these cells phosphoric acid is used as a non-conductive electrolyte to pass positive hydrogen ions from the anode to the cathode. These cells commonly work in temperatures of 150 to 200 degrees Celsius. This high temperature will cause heat and energy loss if the heat is not removed and used properly. This heat can be used to produce steam for air conditioning systems or any other thermal energy consuming system. Using this heat in cogeneration can enhance the efficiency of phosphoric acid fuel cells from 40–50% to about 80%. Phosphoric acid, the electrolyte used in PAFCs, is a non-conductive liquid acid which forces electrons to travel from anode to cathode through an external electrical circuit. Since the hydrogen ion production rate on the anode is small, platinum is used as catalyst to increase this ionization rate. A key disadvantage of these cells is the use of an acidic electrolyte. This increases the corrosion or oxidation of components exposed to phosphoric acid.

High-temperature fuel cells SOFC

Main article: Solid oxide fuel cell

Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic material called yttria-stabilized zirconia (YSZ), as the electrolyte. Because SOFCs are made entirely of solid materials, they are not limited to the flat plane configuration of other types of fuel cells and are often designed as rolled tubes. They require high operating temperatures (800–1000 °C) and can be run on a variety of fuels including natural gas.

SOFCs are unique since in those, negatively charged oxygen ions travel from the cathode (positive side of the fuel cell) to the anode (negative side of the fuel cell) instead of positively charged hydrogen ions travelling from the anode to the cathode, as is the case in all other types of fuel cells. Oxygen gas is fed through the cathode, where it absorbs electrons to create oxygen ions. The oxygen ions then travel through the electrolyte to react with hydrogen gas at the anode. The reaction at the anode produces electricity and water as by-products. Carbon dioxide may also be a by-product depending on the fuel, but the carbon emissions from an SOFC system are less than those from a fossil fuel combustion plant. The chemical reactions for the SOFC system can be expressed as follows:

Anode Reaction: 2H2 + 2O2− → 2H2O + 4e
Cathode Reaction: O2 + 4e → 2O2−
Overall Cell Reaction: 2H2 + O2 → 2H2O

SOFC systems can run on fuels other than pure hydrogen gas. However, since hydrogen is necessary for the reactions listed above, the fuel selected must contain hydrogen atoms. For the fuel cell to operate, the fuel must be converted into pure hydrogen gas. SOFCs are capable of internally reforming light hydrocarbons such as methane (natural gas), propane and butane. These fuel cells are at an early stage of development.

Challenges exist in SOFC systems due to their high operating temperatures. One such challenge is the potential for carbon dust to build up on the anode, which slows down the internal reforming process. Research to address this “carbon coking” issue at the University of Pennsylvania has shown that the use of copper-based cermet (heat-resistant materials made of ceramic and metal) can reduce coking and the loss of performance. Another disadvantage of SOFC systems is slow start-up time, making SOFCs less useful for mobile applications. Despite these disadvantages, a high operating temperature provides an advantage by removing the need for a precious metal catalyst like platinum, thereby reducing cost. Additionally, waste heat from SOFC systems may be captured and reused, increasing the theoretical overall efficiency to as high as 80%–85%.

The high operating temperature is largely due to the physical properties of the YSZ electrolyte. As temperature decreases, so does the ionic conductivity of YSZ. Therefore, to obtain optimum performance of the fuel cell, a high operating temperature is required. According to their website, Ceres Power, a UK SOFC fuel cell manufacturer, has developed a method of reducing the operating temperature of their SOFC system to 500–600 degrees Celsius. They replaced the commonly used YSZ electrolyte with a CGO (cerium gadolinium oxide) electrolyte. The lower operating temperature allows them to use stainless steel instead of ceramic as the cell substrate, which reduces cost and start-up time of the system.

Hydrogen-oxygen fuel cell

The hydrogen-oxygen fuel cell or alkaline fuel cell was designed and first demonstrated publicly by Francis Thomas Bacon in 1959. It was used as a primary source of electrical energy in the Apollo space program. The cell consists of two porous carbon electrodes impregnated with a suitable catalyst such as Pt, Ag, CoO, etc. The space between the two electrodes is filled with a concentrated solution of KOH or NaOH which serves as an electrolyte. 2H2 gas and O2 gas are bubbled into the electrolyte through the porous carbon electrodes. Thus the overall reaction involves the combination of hydrogen gas and oxygen gas to form water. The cell runs continuously until the reactant’s supply is exhausted. This type of cell operates efficiently in the temperature range 343 K to 413 K and provides a potential of about 0.9 V.

MCFC

Main article: Molten carbonate fuel cell

Molten carbonate fuel cells (MCFCs) require a high operating temperature, 650 °C (1,200 °F), similar to SOFCs. MCFCs use lithium potassium carbonate salt as an electrolyte, and this salt liquefies at high temperatures, allowing for the movement of charge within the cell – in this case, negative carbonate ions.[45]

Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the anode, eliminating the need to produce hydrogen externally. The reforming process creates CO2 emissions. MCFC-compatible fuels include natural gas, biogas and gas produced from coal. The hydrogen in the gas reacts with carbonate ions from the electrolyte to produce water, carbon dioxide, electrons and small amounts of other chemicals. The electrons travel through an external circuit creating electricity and return to the cathode. There, oxygen from the air and carbon dioxide recycled from the anode react with the electrons to form carbonate ions that replenish the electrolyte, completing the circuit. The chemical reactions for an MCFC system can be expressed as follows:

Anode Reaction: CO32− + H2 → H2O + CO2 + 2e
Cathode Reaction: CO2 + ½O2 + 2e → CO32−
Overall Cell Reaction: H2 + ½O2 → H2O

As with SOFCs, MCFC disadvantages include slow start-up times because of their high operating temperature. This makes MCFC systems not suitable for mobile applications, and this technology will most likely be used for stationary fuel cell purposes. The main challenge of MCFC technology is the cells’ short life span. The high-temperature and carbonate electrolyte lead to corrosion of the anode and cathode. These factors accelerate the degradation of MCFC components, decreasing the durability and cell life. Researchers are addressing this problem by exploring corrosion-resistant materials for components as well as fuel cell designs that may increase cell life without decreasing performance.

MCFCs hold several advantages over other fuel cell technologies, including their resistance to impurities. They are not prone to “carbon coking”, which refers to carbon build-up on the anode that results in reduced performance by slowing down the internal fuel reforming process. Therefore, carbon-rich fuels like gases made from coal are compatible with the system. The Department of Energy claims that coal, itself, might even be a fuel option in the future, assuming the system can be made resistant to impurities such as sulfur and particulates that result from converting coal into hydrogen. MCFCs also have relatively high efficiencies. They can reach a fuel-to-electricity efficiency of 50%, considerably higher than the 37–42% efficiency of a phosphoric acid fuel cell plant. Efficiencies can be as high as 65% when the fuel cell is paired with a turbine, and 85% if heat is captured and used in a Combined Heat and Power (CHP) system.

FuelCell Energy, a Connecticut-based fuel cell manufacturer, develops and sells MCFC fuel cells. The company says that their MCFC products range from 300 kW to 2.8 MW systems that achieve 47% electrical efficiency and can utilize CHP technology to obtain higher overall efficiencies. One product, the DFC-ERG, is combined with a gas turbine and, according to the company, it achieves an electrical efficiency of 65%.

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