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Fuel Cell Handbook - Fourth Edition
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Fuel Cell Handbook - Fourth Edition
6. Polymer Electrolyte Fuel Cell
FUEL CELL DESCRIPTION.1-1 1.2 CELL STACKING .1-7 1.3 FUEL CELL PLANT DESCRIPTION.1-8 1.4 CHARACTERISTICS.1-9 1.5 ADVANTAGES/DISADVANTAGES .1-11 1.6 APPLICATIONS, DEMONSTRATIONS, AND STATUS .1-13 1.6.1 Stationary Electric Power .1-13 1.6.2 Vehicle Motive Power .1-20 1.6.3 Space and Other Closed Environment Power.1-21 1.6.4 Derivative Applications .1-22 1.7 REFERENCES .1-22
2. FUEL CELL PERFORMANCE.2-1 2.1
PRACTICAL THERMODYNAMICS.2-1 2.1.1 Ideal Performance .2-1 2.1.2 Actual Performance.2-4 2.1.3 Fuel Cell Performance Variables .2-9 2.1.4 Cell Energy Balance .2-16 2.2 SUPPLEMENTAL THERMODYNAMICS.2-17 2.2.1 Cell Efficiency .2-18 2.2.2 Efficiency Comparison to Heat Engines .2-19 2.2.3 Gibbs Free Energy and Ideal Performance .2-20 2.2.4 Polarization: Activation (Tafel) and Concentration or Gas Diffusion Limits.2-24 2.3 REFERENCES .2-27
3. PHOSPHORIC ACID FUEL CELL .3-1 3.1
CELL COMPONENTS.3-2 3.1.1 State-of-the-Art Components .3-2 3.1.2 Development Components .3-5 3.2 PERFORMANCE.3-10 3.2.1 Effect of Pressure.3-10 3.2.2 Effect of Temperature .3-11 3.2.3 Effect of Reactant Gas Composition and Utilization.3-12 3.2.4 Effect of Impurities .3-14 3.2.5 Effects of Current Density .3-18 3.2.6 Effects of Cell Life.3-19 3.3 SUMMARY OF EQUATIONS FOR PAFC.3-19 3.4 REFERENCES .3-20
4. MOLTEN CARBONATE FUEL CELL .4-1 4.1
CELL COMPONENTS.4-4 4.1.1 State-of-the-Art.4-4 4.1.2 Development Components .4-9 4.2 PERFORMANCE.4-13 4.2.1 Effect of Pressure.4-15 4.2.2 Effect of Temperature .4-18 ii 4.2.3 Effect of Reactant Gas Composition and Utilization.4-20 4.2.4 Effect of Impurities .4-24 4.2.5 Effects of Current Density .4-29 4.2.6 Effects of Cell Life.4-29 4.2.7 Internal Reforming .4-30 4.3 SUMMARY OF EQUATIONS FOR MCFC .4-33 4.4 REFERENCES .4-37
5. SOLID OXIDE FUEL CELL.5-1 5.1
CELL COMPONENTS.5-3 5.1.1 State-of-the-Art.5-3 5.1.2 Cell Configuration Options.5-6 5.1.3 Development Components .5-11 5.2 PERFORMANCE.5-15 5.2.1 Effect of Pressure.5-16 5.2.2 Effect of Temperature .5-17 5.2.3 Effect of Reactant Gas Composition and Utilization.5-19 5.2.4 Effect of Impurities .5-22 5.2.5 Effects of Current Density .5-23 5.2.6 Effects of Cell Life.5-24 5.3 SUMMARY OF EQUATIONS FOR SOFC40.5-25 5.4 REFERENCE.5-25
6. POLYMER ELECTROLYTE FUEL CELL.6-1 6.1
CELL COMPONENTS.6-1 6.1.1 Water Management .6-2 6.1.2 State-of-the-Art Components .6-3 6.1.3 Development Components .6-6 6.2 PERFORMANCE.6-9 6.3 DIRECT METHANOL PROTON EXCHANGE FUEL CELL.6-12 6.4 REFERENCE.6-13
SYSTEM PROCESSES.7-2 7.1.1 Fuel Processors .7-2 7.1.2 Rejected Heat Utilization.7-7 7.1.3 Power Conditioners and Grid Interconnection.7-8 7.1.4 System and Equipment Performance Guidelines .7-10 7.2 SYSTEM OPTIMIZATIONS .7-12 7.2.1 Pressurization .7-12 7.2.2 Temperature.7-14 7.2.3 Utilizations.7-15 7.2.4 Heat Recovery.7-16 7.2.5 Miscellaneous .7-17 7.2.6 Concluding Remarks on System Optimization.7-17 7.3 FUEL CELL SYSTEM DESIGNS - PRESENT.7-18 7.3.1 Natural Gas Fueled PEFC System .7-18 7.3.2 Natural Gas Fueled PAFC System.7-19 7.3.3 Natural Gas Fueled Externally Reformed MCFC System .7-22 7.3.4 Natural Gas Fueled Internally Reformed MCFC System .7-24 7.3.5 Natural Gas Fueled Pressurized SOFC System .7-25 iii 7.4 FUEL CELL SYSTEM DESIGNS - CONCEPTS FOR THE FUTURE .7-28 7.4.1 UltraFuelCell, A Natural Gas Fueled Multi-Stage Solid State Power Plant System .7-29 7.4.2 Natural Gas Fueled Multi-Stage MCFC System .7-33 7.4.3 Coal Fueled SOFC System (Vision 21).7-33 7.4.4 Coal Fueled Multi-Stage SOFC System (Vision 21).7-37 7.4.5 Coal Fueled Multi-Stage MCFC System (Vision 21).7-37 7.5 RESEARCH AND DEVELOPMENT.7-37 7.5.1 Natural Gas Fueled Pressurized SOFC System .7-37 7.5.2 UltraFuelCell, A Natural Gas Fueled Multi-Stage Solid State Power Plant System.7-38 7.5.3 Natural Gas Fueled Multi-Stage MCFC System .7-41 7.5.4 Coal Fueled Multi-Stage SOFC System (Vision 21).7-41 7.5.5 Coal Fueled Multi-Stage MCFC System (Vision 21).7-41 7.6 REFERENCE.7-41
8. SAMPLE CALCULATIONS.8-1 8.1
UNIT OPERATIONS.8-1 8.1.1 Fuel Cell Calculations .8-1 8.1.2 Fuel Processing Calculations .8-16 8.1.3 Power Conditioners .8-20 8.1.4 Others.8-20 8.2 SYSTEM ISSUES.8-21 8.2.1 Efficiency Calculations.8-21 8.2.2 Thermodynamic Considerations.8-23 8.3 SUPPORTING CALCULATIONS.8-27 8.4 COST CALCULATIONS .8-35 8.4.1 Cost of Electricity .8-35 8.4.2 Capital Cost Development .8-36 8.5 COMMON CONVERSION FACTORS .8-37 8.6 REFERENCES .8-38
9. APPENDIX.9-1 9.1 EQUILIBRIUM CONSTANTS.9-1 9.2 CONTAMINANTS FROM COAL GASIFICATION.9-2 9.3
SELECTED MAJOR FUEL CELL REFERENCES, 1993 TO PRESENT.9-4 9.4
Figure 3-4 Polarization at Cathode (0.52 mg Pt/cm2) as a Function of O2 Utilization, which is Increased by Decreasing the Flow Rate of the Oxidant at Atmospheric Pressure 100% H3PO4, 191?C, 300 mA/cm2, 1 atm. (38) .3-13 Figure 3-5 Influence of CO and Fuel Gas Composition on the Performance of Pt Anodes in 100% H3PO4 at 180?C. 10% Pt Supported on Vulcan XC-72, 0.5 mg Pt/cm2 Dew Point, 57? Curve 1, 100% H2; Curves 2-6, 70% H2 and CO2/CO Contents (mol%) Specified (21).3-17 Figure 3-6 Effect of H2S Concentration: Ultra-High Surface Area Pt Catalyst (37).3-17 Figure 3-7 Reference Performances at 8.2 atm and Ambient Pressure (16) .3-20 Figure 4-1 Dynamic Equilibrium in Porous MCFC Cell Elements (Porous electrodes are depicted with pores covered by a thin film of electrolyte).4-3 Figure 4-2 Progress in the Generic Performance of MCFCs on Reformate Gas and Air (11,12) .4-5 Figure 4-3 Effect of Oxidant Gas Composition on MCFC Cathode Performance at 650?C, (Curve 1, 12.6% O2/18.4% CO2/69.0% N2; Curve 2, 33% O2/67% CO2) (49, Figure 3, Pg. 2712) .4-14 Figure 4-4 Voltage and Power Output of a 1.0/m2 19 cell MCFC Stack after 960 Hours at 965?C and 1 atm, Fuel Utilization, 75% (50) .4-14 Figure 4-5 Influence of Cell Pressure on the Performance of a 70.5 cm2 MCFC at 650?C (anode gas, not specified; cathode gases, 23.2% O2/3.2% CO2/66.3% N2/7.3% H2O and 9.2% O2/18.2% CO2/65.3% N2/7.3% H2O; 50% CO2, utilization at 215 mA/cm2) (53, Figure 4, Pg. 395) .4-17 Figure 4-6
Influence of Pressure on Voltage Gain (55).4-18 Figure 4-7 Effect of CO2/O2 Ratio on Cathode Performance in an MCFC, Oxygen Pressure is 0.15 atm (20, Figure 5-10, Pgs. 5-20).4-21 Figure 4-8 Influence of Reactant Gas Utilization on the Average Cell Voltage of an MCFC Stack (67, (Figure 4-21, Pgs. 4-24) .4-22 Figure 4-9 Dependence of Cell Voltage on Fuel Utilization (69) .4-24 Figure 4-10 Influence of 5 ppm H2S on the Performance of a Bench Scale MCFC v (10 cm x 10 cm) at 650?C, Fuel Gas (10% H2/5% CO2/10% H2O/75% He) at 25% H2 Utilization (78, Figure 4, Pg. 443) .4-28 Figure 4-11 IIR/DIR Operating Concept, Molten Carbonate Fuel Cell Design (42).4-31 Figure 4-12 CH4 Conversion as a Function of Fuel Utilization in a DIR Fuel Cell.4-32 Figure 4-13 Voltage Current Characteristics of a 3kW, Five Cell DIR Stack with 5,016 cm2 Cells Operating on 80/20% H2/CO2 and Methane (85) .4-33 Figure 4-14 Performance Data of a 0.37m2 2 kW Internally Reformed MCFC Stack at 650?C and 1 atm (12).4-33 Figure 4-15 Average Cell Voltage of a 0.37m2 2 kW Internally Reformed MCFC Stack at 650?C and 1 atm. Fuel, 100% CH4, Oxidant, 12% CO2/9% O2/77% N2 (12).4-34 Figure 4-16 Model Predicted and Constant Flow Polarization Data Comparison (94) .4-36 Figure 5-1 Solid Oxide Fuel Cell Designs at the Cathode .5-2 Figure 5-2 Solid Oxide Fuel Cell Operating Principle (2) .5-2 Figure 5-3 Cross Section (in the Axial Direction of the +) of an Early Tubular Configuration for SOFCs [(8), Figure 2, p. 256] .5-8 Figure 5-4 Cross Section (in the Axial Direction of the Series-Connected Cells) of an Early "Bell and Spigot" Configuration for SOFCs [(15), Figure 24, p. 332] .5-8 Figure 5-5 Cross Section of Present Tubular Configuration for SOFCs (2) .5-9 Figure 5-6 Gas-Manifold Design for a Tubular SOFC (2).5-9 Figure 5-7
Cell-to-Cell Connections Among Tubular SOFCs (2).5-10 Figure 5-8 Single Cell Performance of LSGM Electrolyte (500 mm thick) (34) .5-14 Figure 5-9 Effect of Pressure on AES Cell Performance at 1000?C [(24) 2.2 cm diameter, 150 cm active length] .5-16 Figure 5-10 Two Cell Stack Performance with 67% H2 + 22% CO + 11% H2O/Air (20) .5-17 Figure 5-11 Two Cell Stack Performance with 97% H2 and 3% H2O/Air (41) .5-19 Figure 5-12 Cell Performance at 1000?C with Pure Oxygen (o) and Air (D) Both at 25% Utilization (Fuel (67% H2/22% CO/11%H2O) Utilization is 85%) (42).5-20 Figure 5-13 Influence of Gas Composition of the Theoretical Open-Circuit Potential of SOFC at 1000?C [(8) Figure 3, p. 258].5-21 Figure 5-14 Variation in Cell Voltage as a Function of Fuel Utilization and Temperature (Oxidant (o - Pure O2; D - Air) Utilization is 25%. Currently Density is 160 mA/cm2 at 800, 900 and 1000?C and 79 mA/cm2 at 700?C) (42) .5-22 Figure 5-15 SOFC Performance at 1000?C and 350 mA/cm,2 85% Fuel Utilization and 25% Air Utilization (Fuel = Simulated Air-Blown Coal Gas Containing 5000 ppm NH3, 1 ppm HCl and 1 ppm H2S) (47) .5-23 Figure 5-16 Voltage-Current Characteristics of an AES Cell (1.56 cm Diameter, 50 cm Active Length) .5-24 Figure 6-1 PEFC Schematic (19).6-4 Figure 6-2 Performance of Low Platinum Loading Electrodes (23).6-5 Figure 6-3 Multi-Cell Stack Performance on Dow Membrane (31).6-7 Figure 6-4 Effect on PEFC Performances of Bleeding Oxygen into the Anode Compartment (6) .6-9 Figure 6-5 Evolutionary Changes in PEFCs Performance [(a) H2/O2, (b) Reformate Fuel/Air, (c) H2/Air)] [(14, 37, 38)].6-10 Figure 6-6 Influence of O2 Pressure on PEFCs Performance (93?C, Electrode Loadings of 2 mg/cm2 Pt, H2 Fuel at 3 Atmospheres) [(42) Figure 29, p. 49].6-11 Figure 6-7
Cell Performance with Carbon Monoxide in Reformed Fuel (44).6-12 Figure 6-8 Single Cell Direct Methanol Fuel Cell Data (45) .6-13 Figure 7-1 A Rudimentary Fuel Cell Power System Schematic.7-1 Figure 7-2 Optimization Flexibility in a Fuel Cell Power System.7-13 Figure 7-3 Natural Gas Fueled PEFC Power Plant.7-18 Figure 7-4 Natural Gas fueled PAFC Power System.7-20 vi Figure 7-5 Natural Gas Fueled MCFC Power System.7-22 Figure 7-6 Natural Gas Fueled MCFC Power System.7-24 Figure 7-7 Schematic for a 4.5 MW Pressurized SOFC .7-26 Figure 7-8 Schematic for a 4 MW UltraFuelCell Solid State System .7-30 Figure 7-9 Schematic for a 500 MW Class Coal Fueled Pressurized SOFC.7-34 Figure 9-1 Equilibrium Constants (Partial Pressures in MPa) for (a) Water Gas Shift, (b) Methane Formation, (c) Carbon Deposition (Boudouard Reaction), and (d) Methane Decomposition (J.R. Rostrup-Nielsen, in Catalysis Science and Technology, Edited by J.R. Anderson and M. Boudart, Springer-Verlag, Berlin GDR, p.1, 1984.).9-2 vii LIST OF TABLES AND EXAMPLES Table Title Page Table 1-1 Summary of Major Differences of the Fuel Cell Types .1-5 Table 1-2 Summary of Major Fuel Constituents Impact on PAFC, MCFC, SOFC, and PEFC.1-11 Table 2-1 Electrochemical Reactions in Fuel Cells.2-2 Table 2-2 Fuel Cell Reactions and the Corresponding Nernst Equations .2-3 Table 2-3 Ideal Voltage as A Function of Cell Temperature .2-4 Table 2-4 Outlet Gas Composition as a Function of Utilization in MCFC at 650?C.2-16 Table 3-1
Evolution of Cell Component Technology for Phosphoric Acid Fuel Cells .3-2 Table 3-2 Advanced PAFC Performance .3-6 Table 3-3 Dependence of k(T) on Temperature .3-15 Table 4-1 Evolution of Cell Component Technology for Molten Carbonate Fuel Cells.4-4 Table 4-2 Amount in Mol% of Additives to Provide Optimum Performance (39).4-11 Table 4-3 Qualitative Tolerance Levels for Individual Contaminants in Isothermal Bench-Scale Carbonate Fuel Cells (46, 47, and 48).4-13 Table 4-4 Equilibrium Composition of Fuel Gas and Reversible Cell Potential as a Function of Temperature .4-19 Table 4-5 Influence of Fuel Gas Composition on Reversible Anode Potential at 650?C (68, Table 1, Pg. 385) .4-23 Table 4-6 Contaminants from Coal Derived Fuel Gas and Their Potential Effect on MCFCs (70, Table 1, Pg. 299) .4-25 Table 4-7 Gas Composition and Contaminants from Air-Blown Coal Gasifier After Hot Gas Cleanup, and Tolerance Limit of MCFCs to Contaminants.4-26 Table 5-1 Evolution of Cell Component Technology for Tubular Solid Oxide Fuel Cells .5-4 Table 5-2 K Values for DVT .5-18 Table 7-1 Typical Steam Reformed Natural Gas Product.7-3 Table 7-2 Typical Partial Oxidation Reformed Fuel Oil Product (1).7-5 Table 7-3 Typical Coal Gas Compositions for Selected Oxygen-Blown Gasifiers .7-7 Table 7-4 Equipment Performance Assumptions.7-11 Table 7-5 Stream Properties for the Natural Gas Fueled Pressurized SOFC .7-20 Table 7-6 Operating/Design Parameters for the NG fueled PAFC . 21 Table 7-7
Performance Summary for the NG fueled PAFC .21 Table 7-8 Stream Properties for the Natural Gas Fueled MC Power ER-MCFC.7-22 Table 7-9 Performance Summary for the NG Fueled ER-MCFC.7-23 Table 7-10 Operating/Design Parameters for the NG Fueled IR-MCFC .7-25 Table 7-11 Overall Performance Summary for the NG Fueled IR-MCFC.7-25 Table 7-12 Stream Properties for the Natural Gas Fueled Pressurized SOFC .7-26 Table 7-13 Operating/Design Parameters for the NG Fueled Pressurized SOFC .7-28 Table 7-14 Overall Performance Summary for the NG Fueled Pressurized SOFC .7-28 Table 7-15 Heron Gas Turbine Parameters.7-28 Table 7-16 Example Fuel Utilization in a Multi-Stage Fuel Cell Module .7-29 Table 7-17 Stream Properties for the Natural Gas Fueled UltraFuelCell Solid State Power Plant System .7-30 Table 7-18 Operating/Design Parameters for the NG fueled UltraFuelCell System .7-32 Table 7-19 Overall Performance Summary for the NG fueled UltraFuelCell System.7-33 Table 7-20 Stream Properties for the 500 MW Class Coal Gas Fueled Cascaded SOFC.7-34 Table 7-21 Coal Analysis.7-36 Table 7-22
Operating/Design Parameters for the Coal Fueled Pressurized SOFC .7-36 Table 7-23 Overall Performance Summary for the Coal Fueled Pressurized SOFC.7-37 Example 8-1 Fuel Flow Rate for 1 Ampere of Current (Conversion Factor Derivation).8-1 Example 8-2 Required Fuel Flow Rate for 1 MW Fuel Cell .8-2 Example 8-3 PAFC Effluent Composition .8-4 Example 8-4 MCFC Effluent Composition - Ignoring the Water Gas Shift Reaction.8-7 Example 8-5 MCFC Effluent Composition - Accounting for the Water Gas Shift Reaction.8-9 Example 8-6 SOFC Effluent Composition - Accounting for Shift and Reforming Reactions.8-12 Example 8-7 Generic Fuel Cell - Determine the Required Cell Area, and Number of Stacks .8-15 Example 8-8 Methane Reforming - Determine the Reformate Composition.8-16 Example 8-9 Methane Reforming - Carbon Deposition .8-19 Example 8-10 Conversion between DC and AC Power .8-20 Example 8-11 LHV, HHV Efficiency and Heat Rate Calculations.8-21 Example 8-12 Efficiency of a Cogeneration Fuel Cell System .8-23 Example 8-13 Production of Cogeneration Steam in a Heat Recovery Boiler (HRB).8-23 Example 8-14 Molecular Weight Calculation for Air .8-27 Table 8-1 Common Atomic Elements and Weights.8-28 Example 8-15 Molecular Weight, Density and Heating Value Calculations .8-28 Table 8-2 HHV Contribution of Common Gas Constituents.8-30 Example 8-16 Heat Capacities .8-32 Table 8-3 Ideal Gas Heat Capacity Coefficients for Common Fuel Cell Gases.8-33 Example 8-17 Cost of Electricity.8-35 Table 8-4 Distributive Estimating Factors .8-36 Table 9-1 Typical Contaminant Levels Obtained from Selected Coal Gasification Processes .9-3
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