Fuel Cell Handbook - Fourth Edition

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Fuel Cell Handbook - Fourth Edition

200 pages
published 1998

List of Figures
List of Tables and Examples
1. Technology Overview
2. Fuel Cell Performance
3. Phosphoric Acid Fuel Cell
4. Molten Carbonate Fuel Cell
5. Solid Oxide Fuel Cell
6. Polymer Electrolyte Fuel Cell
7. Fuel Cell Systems
8. Sample Calculations
9. Appendix
10. Index

Table of Contents
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1.TECHNOLOGY OVERVIEW.1-1 1.1
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

7. FUEL CELL SYSTEMS.7-1 7.1
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

LIST OF SYMBOLS.9-7 10.

INDEX.10-1 iv

LIST OF FIGURES Figure Title Page Figure 1-1 Schematic of an Individual Fuel Cell.1-1 Figure 1-2 External Reforming and Internal Reforming MCFC System Comparison.1-6 Figure 1-3 Expanded View of a Basic Fuel Cell Repeated Unit in a Fuel Cell Stack (1) .1-8 Figure 1-4 Fuel Cell Power Plant Major Processes.1-9 Figure 1-5 Relative Emissions of PAFC Fuel Cell Power Plants Compared to Stringent Los Angeles Basin Requirements.1-10 Figure 1-6 Combining the SOFC with a Gas Turbine Engine to Improve Efficiency .1-18 Figure 2-1 H2/O2 Fuel Cell Ideal Potential as a Function of Temperature.2-4 Figure 2-2 Ideal and Actual Fuel Cell Voltage/Current Characteristic .2-5 Figure 2-3 Contribution to Polarization of Anode and Cathode.2-8 Figure 2-4 Flexibility of Operating Points According to Cell Parameters .2-9 Figure 2-5 Voltage/Power Relationship.2-10 Figure 2-6 Dependence of the Initial Operating Cell Voltage of Typical Fuel Cells on Temperature .2-12 Figure 2-7 The Variation in the Reversible Cell Voltage as a Function of Reactant Utilization .2-15 Figure 2-8 Example of a Tafel Plot.2-25 Figure 3-1 Improvement in the Performance of H2-Rich Fuel/Air PAFCs .3-5 Figure 3-2 Advanced Water-Cooled PAFC Performance (16).3-7 Figure 3-3 Effect of Temperature: Ultra-High Surface Area Pt Catalyst. Fuel: H2, H2 + 200 ppm H2S and Simulated Coal Gas (37).3-12

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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