FUEL CELLS

1. Introduction A fuel cell is an electrochemical device (a galvanic cell) which converts free energy of a chemical reaction into electrical energy (electricity) by exploiting the natural tendency of oxygen and hydrogen to react. (1)(2). The byproducts are heat and water if hydrogen and air are the reactants, in some fuel cell types, the additional byproducts may be carbon dioxide and leftover lower forms of hydrocarbons depending on the fossil fuels used(2) . There is no combination in this process and hence no nitrites are produced.(2) A fuel cell produces electricity on demand continuously as long as the fuel and oxidant are supplied. 2. Fuel Cells The components of a fuel cell are anode, anodic catalyst layer, electrolyte, cathodic catalyst layer, cathode, bipolar plates/interconnects and sometimes gaskets for sealing/preventing leakage of gases between anode and cathode. The sack of such fuel cells is connected in series/ parallel connections to yield the desired voltage and current. The anode and cathode consist of porous gas diffusion layers, usually made of highly electron conductivity materials such as porous graphite thin layers. One of the common catalysts is platinum for low temperature fuel cells and nickel for high temperature fuel cells, and other materials depending on the fuel cell type. The electrolyte is made of such material that it provides high proton conductivity and theoretically zero electron conductivity. The charge carriers are different depending on type of fuel cells. (1) The anode reaction in fuel cells is either direct oxidation of hydrogen or methanol or indirect oxidation via a reforming step for hydrocarbon fuels. The cathode reaction is oxygen reduction from air in most fuel cells. (1)

Figure 1: Fuel cell. (3)

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2.1 Solid State Fuel Cell/ Solid Oxide fuel Cell A solid oxide fuel cell is composed of two porous ceramic electrodes and a solid state electrolyte, made of solid metal oxides. For this reason, the SOFC is also referred to as ceramic fuel cell. The typical modern SOFC is composed of an electrolyte made of yttria-stabilized zirconia (YSZ), a porous anode made of nickel and ytrria stabilized zirconia (Ni/YSZ) and a porous cathode composed of doped LaMnO3. High efficiency and fuel adaptability are not the only advantages of solid oxide fuel cells. SOFCs are attractive as energy sources because they are clean, reliable, and almost entirely nonpolluting. Because there are no moving parts and the cells are therefore vibration-free, the noise pollution associated with power generation is also eliminated. (3) 2.2 Working of a Solid-oxide fuel Cell The Solid oxide fuel cell is constructed with two porous electrodes with an electrolyte in between. Air flows along the cathode (which is therefore also called the "air electrode"). When an oxygen molecule contacts the cathode/electrolyte interface, it catalytically acquires four electrons from the cathode and splits into two oxygen ions. The oxygen ions diffuse into the electrolyte material and migrate to the other side of the cell where they encounter the anode (also called the "fuel electrode"). The oxygen ions encounter the fuel at the anode/electrolyte interface and react catalytically, giving off water, carbon dioxide, heat, and electrons. The electrons transport through the anode to the external circuit and back to the cathode, providing a source of useful electrical energy in an external circuit.(1)

Figure 2. Operating concept of a SOFC (9) Two possible design configurations for SOFCs have emerged: a planar design (Figure 3) and a tubular design (Figure 4). In the planar design, the components are assembled in flat stacks, with air and fuel flowing through channels built into the cathode and anode. In the tubular design, components are assembled in the form of a hollow tube, with the cell constructed in layers around a tubular cathode; air flows through the inside of the tube and fuel flows around the exterior.

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Figure 3. Configuration for a planar design SOFC(10)

Figure 4. Configuration for a tubular design SOFC (11) 2.3 Materials Selection and Processing The selection of materials for the individual components in solid oxide fuel cells presents enormous challenges. Each material must have the electrical properties required to perform its function in the cell. There must be enough chemical and structural stability to endure fabrication and operation at high temperatures. The fuel cell needs to run at high temperatures in order to achieve sufficiently high current densities and power output; operation at up to 1000 C is possible using the most common electrolyte material, yttria-stabilized zirconia (YSZ). Reactivity and interdiffusion between the components must be as low as possible. The thermal expansion coefficients of the components must be as close to one another as possible in order to minimize thermal stresses which could lead to cracking and mechanical failure. The air side of the cell must operate in an oxidizing atmosphere and the fuel side must operate in a reducing atmosphere. The temperature and atmosphere requirements drive the materials selection for all the other components. (3) In short the general requirements of the cell components are:1. Electrolyte and interconnect must be fully dense to prevent the mixing of oxidizing and reducing gases, where as the electrodes must be porous to allow gas transport.(1)(3) 2. High electrical conductivity is essential for the electrodes, the electrolyte and the interconnect.
(1)(3)

3. Chemical compatibility is required with the adjoining cell components both during fabrication as well as during cell operation. (1)(3) 4. Each component must have phase, morphological, chemical and dimensional stability. Changes are not desirable at cell operating temperature as well as during long term operation. (1)(3) 5. High thermal and mechanical shock resistance capabilities. (1)(3)

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6. The supporting cell components must have high mechanical strength and toughness at room temperature and during high temperature operation. (1)(3) 7. Thermal expansion co-efficient values must be within a close proximity among all the cell components in order to avoid cracking and to reduce internal stresses during fabrication and cell operation. (1)(3) 8. Low cost and easily available. (1)(3) 2.3.1 Cathode The cathode must meet all the above requirements and be porous in order to allow oxygen molecules to reach the electrode/electrolyte interface. Today the most commonly used cathode material is lanthanum manganite (LaMnO3), a p-type perovskite. Typically, it is doped with rare earth elements (e.g. Sr, Ce, Pr) to enhance its conductivity. Most often it is doped with strontium and referred to as LSM (La 1-xSrxMnO3). The conductivity of these perovskites is all electronic (no ionic conductivity), a desirable feature since the electrons from the open circuit flow back through the cell via the cathode to reduce the oxygen molecules, forcing the oxygen ions through the electrolyte. In addition to being compatible with YSZ electrolytes, it has the further advantage of having adequate functionality at intermediate fuel cell temperatures (about 700 C), allowing it to be used with alternative electrolyte compositions. Any reduction in operating temperature reduces operating costs and expands the materials selection, creating an opportunity for additional cost savings.(3) 2.3.2 Anode The anode must meet most of the same requirements as the cathode for electrical conductivity, thermal expansion compatibility and porosity, and must function in a reducing atmosphere. The reducing conditions combined with electrical conductivity requirements make metals attractive candidate materials. Most development has focused on nickel owing to its abundance and affordability. However, its thermal expansion is too high to pair it in pure form with YSZ; moreover, it tends to sinter and close off its porosity at operation temperatures. These problems have been solved by making the anode out of a NiYSZ composite. The YSZ provides structural support for separated Ni particles, preventing them from sintering together while matching the thermal expansions. Adhesion of the anode to the electrolyte is also improved. 2.3.3 Electrolyte The electrolyte for solid oxide fuel cells must be stable in both reducing and oxidising environments, once the molecular oxygen has been converted to oxygen ions it must migrate through the electrolyte to the fuel side of the cell. In order for such migration to occur, the electrolyte must possess a high ionic conductivity and no electrical conductivity. It must be fully dense to prevent short circuiting of reacting gases through it and it should also be as thin as possible to minimize resistive losses in the cell. As with the other materials, it must be chemically, thermally, and structurally stable across a wide temperature range. In addition the material must be able to be formed into thin, strong film with no gas leaks. Till now stabilised zirconia, especially yttria-stabilised zirconia, which posses the fluorite structure has been the most favoured electrolyte for SOFCs. (3)(4)

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There are several candidate materials other than YSZ like doped cerium oxide, and doped bismuth oxide. But YSZ is the most promising. YSZ has emerged as the most suitable electrolyte material. Yttria serves the dual purpose of stabilizing zirconia into the cubic structure at high temperatures and also providing oxygen vacancies at the rate of one vacancy per mole of dopant. A typical dopant level is 10 mol% yttria.(3) A reliable way to apply the electrolyte is known as electrochemical vapour deposition which offers high purity and a high level of process control. Electrochemical vapour deposition solves the problem of depositing a dense film onto a porous substrate by passing oxygen through the inside of the cathode tube while chlorides of zirconium and yttrium are passed along the outside. They react at the tube surface to form YSZ and, because the reaction comes to the surface from both sides, the porosity is closed off. Once the porosity is closed off, the electrolyte deposition continues, but now the oxygen diffuses through the growing YSZ layer to react with the chlorides, thereby ensuring a highly dense electrolyte layer. The process, while effective, is expensive and capital-intensive. Cerium oxide has also been considered as a possible electrolyte. Its advantage is that it has high ionic conductivity in air but can operate effectively at much lower temperatures (under 700 C); this temperature range significantly broadens the choice of materials for the other components, which can be made of much less expensive and more readily available materials. The problem is that this electrolyte is susceptible to reduction on the anode (fuel) side. At low operating temperatures (500-700 C) grain boundary resistance is a significant impediment to ionic conductivity. Efforts are underway to develop compositions which address these problems. (3) Zirconia Electrolyte Yttria dopes zirconia is the commonly used electrolyte material in SOFCs. Yttria stabilised zirconia (YSZ) having high strength and toughness as the electrolyte in SOFC is desirable. A strong and tough electrolyte is less sensitive to the presence of flaws and imparts better fracture resistance to fuel cell during fabrication and operation. (5) Zirconia exhibits three polymorphs. It has monoclinic structure at room temperature, changing to tetragonal above 1170 C and to the cubic fluorite structure above 2370 C. The addition of dopant such as yttria stabilises the fluorite and tetragonal phase down to room temperature, leading to an increase in the oxide vacancy concentration.(4) The mechanical properties of YSZ electrolyte vary depending on the characteristics of starting powders used in fabrication, the fabrication route and the fabrication conditions. At room temperature YSZ (8mol% Y2O3) has a bending strength of about 300-400 MPa and fracture toughness of about 3MN m3/2. The tetragonal phase with 2.5-3 mol % Y2O3 content has high strength (around 1,000 MPa at RT) but the conductivity is lower. The 9.0-10% ZrO2-Y2O3 compositions are in a single (cubic) phase region and therefore show relatively small decrease in ionic conductivity as a function of time at the operating temperatures of the fuel cell. (5) Inspite of a sustaining search for a suitable electrolyte for SOFCs doped zirconia has been selected as : Isothermal variation of conductivity shows a maximum at 9 mol% of dopant for ZrO2-M2O3 systems. (5)

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The activation energy is close to 0.8eV for the composition of maximum conductivity. (5) For a particular composition, the conductivity increases as the radius of the dopant cation approaches that of Zr 4+. Thus, the best conductivity in Zr-based system is obtained with ZrO2Sc2O3 system. (5) In the working temperature range of SOFCs , a decrease in ionic conductivity with the time is observed.(5)

Zirconia- Availability and Production Zirconia is one of the most common materials in the earths crust. To make zirconia fit enough to act as the electrolyte, it is doped by yttria. Pure zirconia (ZrO2) has a monoclinic structure up to a temperature of about 1446 K, and then it changes to the tetragonal modification. For temperatures higher than 2643 K zirconia adopts a cubic fluorite structure. However, the high temperature phases can be partially or completely stabilized at room temperature by doping with oxides such as yttria (Y2O3), calcia (CaO), or magnesia (MgO). Yttria is the most commonly used dopant for stabilizing the cubic phase of zirconia; a fully (cubic) stabilized zirconia is obtained with a Y2O3 ( >7 mol%) , while a Y2O3-content of about 2-6 mol% gives a partially stabilized zirconia.(12) Cubic stabilized zirconia has improved mechanical and thermal properties such as high strength, toughness, and thermal-shock resistance. Furthermore the addition of substitution cation (Y3+), which have lower valency than zirconium ion (Zr4+), induces the generation of oxygen vacancies for charge compensation. The substitution of Zr4+ with Y3+ causes the negative net charge in the lattice; for every mole of yttria incorporated into the zirconia lattice, the charge neutrality condition is kept by forming an oxygen vacancy. Y2O32YZr+3OxO+VO (12) Where YZr refers to Y in the Zr site with the apparent negative charge, and VO is the vacancy in the oxygen site with double positive charge. OxO is the lattice oxygen, i.e., oxygen in the oxygen site with net charge of zero. The existence of vacancies on the oxygen site gives rise to the high ionic conductivity of YSZ. Oxygen is transported by vacancy diffusion mechanism. The concentration of oxygen vacancy is determined by the concentration of the dopant. (12) 3mol% Yttria stabilized zirconia (ZrO2)0.97(Y2O3)0.03 Tetragonal Fluorite-type structure(6) Zirconium.oxide (Zirconia) ZrO2 Monoclinic(low temperature phase) Fluorite-type structure (6)

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2.3.4 Interconnect In the SOFC, the cells need to be connected together and a mechanism for collection of electrical current needs to be provided, and the interconnects are used for this purpose. The interconnect functions as the electrical contact to the cathode while protecting it from the reducing atmosphere of the anode. (3)(4) The high operating temperature of the cells combined with the severe environments means that interconnects must meet the most stringent requirements of all the cell components: 100% electrical conductivity, no porosity (to avoid mixing of fuel and oxygen), thermal expansion compatibility, and inertness with respect to the other fuel cell components. It will be exposed simultaneously to the reducing environment of the anode and the oxidizing atmosphere of the cathode. (3)(4)

3. Advantages of Solid Oxide Fuel Cells One advantage of SOFC is that hydrogen and carbon dioxide are used as fuel in the cell. This means that SOFC can use many common hydrocarbon fuels such as natural gas, diesel, gasoline and alcohol without the need to reform the fuel into pure hydrogen. In other fuel cells, such as the polymer electrolyte fuel cells that are fueled with pure hydrogen the carbon dioxide is a poison. SOFC have a potentially lower cost due to the absence of precious metals, compared to proton exchange membrane and phosphoric acid fuel cells which use platinum as a catalyst. Some other fuel cell types use liquid electrolytes, similar to battery acid that can have a corrosive effect on components. Since SOFC use one piece solid state ceramic cells, they are easier to maintain due to the lack of this corrosion.(7) 4. Applications of Solid Oxide Fuel Cells Fuel cells will have many uses. SOFC are being targeted for use in power and heat generation for homes and businesses as well as auxiliary power units for electrical systems in vehicles. SOFC also can be linked with a gas turbine, in which the hot, high pressure exhaust of the fuel cell can be used to spin the turbine, generating a second source of electricity. (7) 5. Conclusion SOFCs provide highly efficient, pollution free power generation. Research is going now in the direction of lower-temperature SOFC (600 C) in order to decrease the materials cost, which will enable the use of metallic materials with better mechanical properties and thermal conductivity. (8)

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REFERENCES (1) Suddhasatwa Basu Recent trends in fuel cell science and technology (2) J.vanston, H.Elliot Fuel Cells : A technology Forecast . (3) Eileen J. De Guire Solid oxide fuel cells Article -2003 (4) S.C Singhal, K.Kendall High temperature Solide oxide fuel cells (5) B.Viswanathan, M.A Scibioh Fuel Cells- principles and applications (6) Crystal structure gallery -http://staff.aist.go.jp/nomura-k/english/itscgallary-e.htm (09/20/2011) (7) Solid Oxide Fuel Cells Advantages and Applications of SOFCs The American Ceramic Society - http://www.azom.com/article.aspx?ArticleID=3781 (09/18/2011) (8) Solid Oxide fuel cells - http://en.wikipedia.org/wiki/Solid_oxide_fuel_cell (09/15/2011) (9) Solid State Energy Conversion Alliance (SECA)-A Primer on SOFC Technology http://www.seca.doe.gov (09/25/2011) (10). Solid Oxide Fuel Cell - http://www.spice.or.jp/~fisher/sofc.html#descript (09/27/2011) (11) Tubular design SOFC- http://www.pg.siemens.com/en/fuelcells/sofc/tubular/index.cfm (09/27/2011) (12) Oxygen Ion Conductivity in Ytrria Stabilized Zirconia- http://electronicstructure.wikidot.com (10/01/2011) (13) A.B. Hart, G.J, Womack Fuel cells- Theory and Application (14) J.OM Bockris, S. Srinivasan Fuel Cells: Their Electrochemistry

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