SOLID OXIDE FUEL CELLS

G. Bala Murugan* and R. Manoj#

Department of Electrical and Electronics Engineering Anna University of Technology Madurai Dindigul Campus, Dindigul, Tamilnadu, India
*

balamurugan.1392@gmail.com # manoj.r91@gmail.com

Abstract Solid oxide fuel cells (SOFCs) are a type of fuel cells which is made up of ceramic materials. It uses hydrogen or hydrocarbon fuel and oxidizes it using atmospheric oxygen. It operates at very high temperatures such as 500-1000C. A wide range of ceramic materials are used in the SOFCs as anodes, cathodes and electrolytes. It is not poisoned by CO but by sulphur. The new anode materials are created in order to reduce the sulphur poisoning. This cell requires a long time initial heating. This makes it is implementation harder. New low temperature SOFCs are being created to overcome this hurdle. This low temperature SOFCs has their own advantages and disadvantages. Keywords: Solid oxide fuel cell, Yttria Stabilized Zirconia, Polymer electrolyte membrane fuel cells, Lanthanum Strontium Manganite, Ni-YSZ cermet, Intermediate temperature SOFC.
INTRODUCTION

Solid oxide fuel cells has four layers, three of them are ceramics. Those four layers are: Anode, Electrolyte, Cathode, and Cell interconnect. These four layers stacked together measures a few millimetres thick. Hundreds of these cells are connected in series and parallel to form a SOFC stack. Figure 1 shows the typical layout of a SOFC. Nowadays researchers are concentrating in solid oxide fuel cell because of its advantages [1], [2], [4].
WORKING PRINCIPLE

Fuel cell is an electrochemical cell which converts source fuel into electrical energy by using electrochemical reactions[5]. Solid oxide fuel cell is a type of fuel cell which uses solid electrolyte, usually ceramic materials. Solid oxide fuel cells are desired for their capability to use a wide range of fuels including hydrogen, natural gas and many other hydro-carbons. In addition to that they are not poisoned by carbon monoxide as in PEMFCs. Using this type of fuel cell can be a solution for the pollution effects of the fossil fuel energy. Researches are conducted about this fuel cell to improve the working and output of this fuel cell.
STRUCTURE

SOFCs work at very high temperatures, typically between 500 and 1000C. So the cell stack should be heated uniformly and in a well regulated manner. Because the ceramic materials used in this cell has non-uniform thermal expansion. The ceramics in the SOFCs behaves ionically and chemically active only at this temperature range. At these high temperatures reduction of oxygen into oxygen ion occurs at cathode. These ions diffuse through the solid oxide electrolyte to the anode, where they can electrochemically oxidize the fuel, usually hydrogen. In this reaction the by-product is only water, which doesnt pollute the environment. Two electrons are also released as the product of this reaction. These electrons are not allowed to diffuse through the electrolyte due to the nature of the electrolyte. So, these electrons flow through an external circuit where they can do work[5]. The cycle then repeats as those electrons enter the cathode material again. If the fuel is a light hydrocarbon anode also acts as a catalyst for steam which reforms the fuel into hydrogen. The reactions are given below. Reactions at Cathode
1 2

O 2 + 2e O

Reactions at Anode
H 2 + O 2 H 2 O + 2 e

Net reaction

1 O 2 H 2O 2

Figure 1

These reactions are highly exothermic and so the temperature of the cell is kept high. As metal catalysts like platinum is not used the reaction is not affected by Carbon Monoxide. But the ceramic

materials used undergo poisoning with sulphur. So, the fuel to be used should be free from sulphur or it must be filtered before using in the cell.
MATERIALS USED AS ANODE

Sulphur tolerant anode materials The SOFCs utilize Ni-YSZ cermet anodes are susceptible to poisoning by sulphur contents as low as 2 ppm H2S at 1000C. While the performance loss is reversible atH2S concentration less than 15 ppm, the poisoning effect becomes more significant at low temperatures. It is desired to develop the anode materials that are not deactivated by sulphur containing fuel gases. The desired sulphur tolerant anode materials should be electronically conductive, chemically and thermally stable and catalytically active for oxidising H2S, H2 and CO. Calcium-Yttria-Ferrite(CYF) based sulphide material can be obtained by exposing CYF to gas mixture of H2 and H2S at 900C. Then this is lithiated to obtain lithiated sulphide. This material shows a good sulphur tolerance. However the catalytic activity and long-term stability of this material is not yet studied. The Cu-CeO2-YSZ anodes operated at low temperature have high sulphur tolerance. This material can withstand up to 450 ppm of sulphur level without any effect[4]. But, at higher concentrations of sulphur, anode failure occurs. This is due to the reaction of CeO2 with H2S to form Ce2O2S. Sr-La-TiO3/YSZ anode has shown no degradation in the presence of H2S up to 500 ppm in 1000C.
MATERIALS USED AS CATHODE

The ceramic anode layer must be very porous to allow the fuel to flow towards the electrolyte. It must conduct the electrons to the external circuit. The most common material used is cermet which is made up of nickel mixed with YSR (Yttria Stabilized Zirconia)-the common electrolyte material in SOFC. The anode is the thickest and strongest layer in the cell as it provides the mechanical support to the cell stack. Ni-YSZ cermet anode materials The Ni in the cermet anode provides electronic conductivity and catalytic activity for direct oxidation and steam reforming of hydrocarbons. The YSR provides a thermal expansion match for the anode with electrolyte. NiO and YSZ do not form homogeneous solid solution. NiO and YSZ are sintered to form NiO-YSZ composite. This composite is reduced to form porous Ni-YSZ cermet. This material fulfils most requirements of the anode. But this material has some disadvantages: poor redox stability, low tolerance to sulphur, carbon deposition when used with hydrocarbon fuels and nickel agglomeration after using for long time. The carbon deposition with hydrocarbon fuels make this as an unsuitable material for using with hydrocarbon fuels. As nickel is a strong catalyst for the catalytic reaction of steam reforming and direct oxidation of the hydrocarbons, carbon deposits at the anode when excess amount of steam is not available for steam reforming. To solve the problems of carbon deposits several methods are employed. Firstly, the carbon deposits can be avoided by reducing operating temperature. It is found that the carbon arising from the dissociation of CH4 is not deposited on many oxides until the temperature exceeds above 750C. Depositing a thin layer of ceria porous film between YSZ electrolyte and Ni-YSZ anode results in indepostion of carbon. But ceria is successful only methane and at relatively low temperatures. Secondly it can be avoided by improving the present anode materials. A composite anode consisting of Cu-CeO2YSZ/SDC has shown that the addition of CeO2 to CuYSZ/SDC cermet significantly improved the performance of the cell, particularly with hydrocarbon fuels. Replacing nickel cermets with composites containing Cu and ceria or samariadoped-ceria will have a good effect[4]. Unlike Ni, Cu is not catalytically active for carbon deposition but is an effective current collector. However Cu is not as electrocatalytically active as Ni. In addition Cu is a relatively low melting point metal which makes it unfit for standard high temperature SOFCs.

The cathode or air electrolyte is a thin porous layer on the electrolyte. It reduces the oxygen. The cathode material must be electrically conductive. The severe environmental conditions experienced by cathode during operation greatly reduce the number of likely cathode materials. In particular, the cathode material must be stable at the operating temperature in air, it must have high electronic conductivity, high catalytic activity for oxygen molecule dissociation and oxygen reduction and a thermal expansion compatible with the SOFC electrolyte. Chemical interactions with the electrolyte and interconnect materials must be minimal. In addition the cathode material must have porous structure so that the gaseous oxygen can readily diffuse through the cathode to cathode-electrolyte interface. This porous nature must remain unchanged or unaffected during SOFC operation over the life time of the stack. Lanthanum Strontium Manganite Lanthanum Strontium Manganite (LSM) is the cathode for commercial use because of its compatibility with electrolyte materials. It has similar coefficient of thermal expansion to YSZ and thus limits the stresses built up due to coefficient of thermal expansion mismatch. It has higher stability in the working environment of air. Also LSM has low chemical reactivity with YSZ which extends the lifetime of the cell. But the LSM is poor ionic conductor which limits the electrochemically active region into the triple phase boundary

where the electrolyte, air and electrode meet. Moreover, LSM cannot be used in lower temperature ranges, because LSM have low ionic conductivity and slow surface oxygen exchange kinetics in this lower temperature region. Cathodes for low temperature SOFCs Composite materials made with mixing lanthanum with metals such as cobalt, iron and nickel are better choice for low temperature SOFC cathodes. They offer higher oxygen diffusion rates and faster reduction kinetics at the electrode than LSM. The Lanthanum Strontium Ferrite (LSF) is a better cathode for low temperature SOFCs. They give good results at 750C. But these materials are still under research[1].
MATERIALS USED AS ELECTROLYTE

The electrolyte is the dense layer made up of ceramic material that conducts oxygen ions from cathode to anode. Its electronic conductivity must be kept as low as possible to prevent the electrons to flow to the cathode directly from the anode which causes leakage current and therefore causes losses. The high operating temperatures of SOFCs allow the kinetics of the oxygen ion transport to be sufficient for good performance. The efficiency of the SOFC increases with the increasing ionic conductivity of the electrolyte. Because virtually, all of the internal resistance in a cell is attributable to electrical resistance loss caused by resistance in electrolyte. In high temperature SOFCs much research has been done on YSZ as the electrolyte, nickel-zirconia cermet as the fuel

electrode material, lanthanum magnite as the air electrode material and lanthanum chromate as the separator. However materials with high oxygen ion conduction such as scandiastabilized zirconia (SSZ), lanthanum gallate and others have been the object of intensive research as non-YSZ electrolytes in recent years. In addition to these electrolytes research is also being done on various hydrogen ion conductors such as barium cerate, strontium cerate and related materials. These types of materials are something different from the oxygen ion conducting materials. In these materials, hydrogen fuel is oxidized at the anode and the H+ ions are conducted from anode to cathode, where they react with oxygen from the air to form H2O. In these materials, electrolyte is having the property that it doesnt allow the electrons from flowing from anode to cathode so the electrons flow through outer circuit where they used to do work. Even today YSZ continues to be the most important electrolyte. SSZ and LaGaO3 are promised materials for application as electrolytes for medium temperature SOFCs operating at below 750C. The materials used in the SOFCs in various periods of time are tabulated in Table I.
INTERMEDIATE TEMPERATURE SOLID OXIDE FUEL CELLS

The intermediate range SOFCs has the working temperature between 550 and 800C. Reducing the operating temperature helps to reduce the cost of the stack. Reducing the working temperature of the cell has both beneficial and detrimental effects. But the net effect is beneficial, particularly regarding operating cost. The significant obstacle is that a set of fully compatible materials have not been developed for

TABLE I MATERIALS USED IN SOFC IN VARIOUS PERIODS OF TIME

CELL COMPONENTS

1965

1975

CURRENT STATUS

Anode

Porous platinum.

Ni/ZrO2 cermet.

Ni/ZrO2 cermet. Composites of CuCeria. Composites of CuSamaria doped ceria. Lanthanum Strontium manganite. Lanthanum Strontium Ferrite. Yttria Stabilized Zirconia. Scandia Stabilized Zirconia. Barium cerate. Strontium cerate. Doped lanthanum chromite.

Cathode

Porous platinum.

Stabilized zirconia and covered with SnO doped with Ln2O3.

Electrolyte

Yttria Stabilized Zirconia.

Yttria Stabilized Zirconia.

Cell Interconnect

Platinum.

Manganese doped Cobalt chromite.

operation in this temperature range. The materials are still under research[3]. Beneficial effects of intermediate temperature SOFCs

SOFCs can be used as an alternative choice for rural energy needs such as remote locations where power grids cannot be established. The emission of hydrogen fuel SOFC is only water. So it can be used as a green energy. SOFCs are more efficient than the IC engines or any other fuel to energy converting systems. SOFCs can be used to run vehicles with which we can control easily without variety of instruments unlike IC engines which need multiple gear boxes and torque converters. SOFCs work silently and quietly unlike the IC engines which produce more vibrations. They can be used as energy supplying systems in space shuttles during space explorations. SOFCs are desirable than PEMFCs because they dont undergo carbon monoxide poisoning. There is no noble metal as in PEMFCs, so the fabrication cost is relatively low. Though PEMFCs work at low temperature, to use hydro carbon fuels, the hydrocarbon reformer must operate at higher temperature than SOFCs.

At this temperature range, reforming of hydrocarbon fuels and removal of sulphur are relatively easier. Using low temperature, the thermal stress can be reduced which improves the properties of the materials. A wide range of materials can be employed at this low temperature range for different stack designs. At lower temperature the heat loss from the stack due to thermal radiation is relatively less. Because energy dissipated through thermal radiation is a function of T4. This also helps in maintaining the sustainability of the cell reactions. Using lower operating temperature results in easier start-up of the cell stack. This helps in reducing the time to reach operating temperature. In lower operating temperatures the undesired thermally activated processes like chromium vapourization, interdiffusion and migration of materials, metallic corrosion effects which are the reasons for the aging of the ceramic materials of the cell stack. In lower temperatures the carbon deposition at anode which occurs due to the usage of hydrocarbon fuels, will also be low.

DEMERITS OF SOFC

SOFCs require heating at start up to achieve their working temperature. Due to nonuniform thermal expansion of the ceramics used, the heating must be uniform and well regulated. As it require highly uniform heating, the heating time will be high, which results in the longer start up time. The initial and operating costs are high as there were not improved technologies. The commonly used SOFC materials are subject to sulphur poisoning. The carbon deposition is the major drawback in using hydrocarbon fuels in SOFCs. Mass storage of hydrogen without high-tech methods is risky.

Detrimental effects of intermediate temperature SOFCs For an identical stack the overall cell voltage will be lower as the temperature decreases. This is due to decreased kinetics, diffusion and ionic conductivity. At low temperatures, the sulphur poisoning effect when using hydrocarbon fuels is relatively high and become more significant. The materials which are said to be used in lower temperatures are not proved to be suitable. Only materials at 800-1100C exist.

MERITS OF SOFC

SOFCs are a solution for the energy crisis in using fossil fuels as they will be extinct one day.

CONCLUSIONS

SOFCs may be a better substitute for the fossil fuel methods today. It prevents environmental pollution which causes many adverse effects like global warming, green house effect etc. It can be implemented as a green technology. It can be an alternative choice for electrical energy in rural areas. The wide range of fuel acceptance of the SOFC makes it more convenient for practical applications. Though it has some drawbacks like sulphur poisoning and carbon deposition in anode, they can be rectified by new materials and methods, which are under research and development. The heating requirement at start up makes it harder to implement and use. By inventing low temperature SOFC materials, this can be overcome. The storage and transportation of hydrogen fuel may be risky at todays situation. But if the researches to store hydrogen fuel in carbon nano tubes, this problem can be solved. It is sure that the SOFCs will have a major impact in the development of human life.
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