Comas Haynes

Assoc. Mem. Asme e-mail: comas.haynes@gtri.gatech.edu Georgia Tech Center for Innovative Fuel Cell and Battery Technologies, Georgia Tech Research Institute, Atlanta, GA 30332-0853

Enhancing the Performance Evaluation and Process Design of a Commercial-Grade Solid Oxide Fuel Cell via Exergy Concepts
Fuel cell technology is a promising means of energy conversion. As the technology matures, process design and analysis are gaining importance. The conventional measures of fuel cell performance (i.e., gross real and voltage efciencies) are limited indices-ofmerit. Contemporary second law concepts (availability/exergy, irreversibility, exergetic efciency) have been used to enhance fuel cell evaluation. A previously modeled solid oxide fuel cell has been analyzed using both conventional measures and the contemporary thermodynamic measures. Various cell irreversibilities were quantied, and their impact on cell inefciency was better understood. Exergetic efciency is more comprehensive than the conventional indices-of- performance. This parameter includes thermal irreversibilities, considers the value of efuent exergy, and has a consistent formulation. Usage of exergetic efciency led to process design discoveries different from the trends observed in conjunction with the conventional efciency measures. The decision variables analyzed were operating pressure, air stoichiometric number (inverse equivalence ratio), operating voltage and fuel utilization. DOI: 10.1115/1.1467647

William J. Wepfer
Fellow ASME e-mail: bill.wepfer@me.gatech.edu The George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0405

Introduction
Solid oxide fuel cells SOFCs are direct energy converters with great promise. The technology has features that distinguish it from other fuel cells. SOFCs are solid state, ceramic cells that currently operate at a nominal temperature of 1000C. Their high operating temperature precludes the need for expensive catalytic surfaces. Carbon monoxide, which is a by-product gas present in hydrogenrich synthesis fuel mixtures, is not harmful to the cells but can be used as a fuel, primarily via shift to hydrogen. The cells reject high quality heat, which can be used for a number of duties i.e., fuel processing, thermal energy for heat engines, etc.. Additionally, the solid electrolyte precludes management issues often encountered with liquids e.g., volatility, corrosion, composition change. Finally, the all solid-state cell allows for novel geometries. Largely due to its seal-less feature, the tubular design is the most mature, and thus the most market-ready, of the SOFCs. Figure 1 illustrates the design of SiemensWestinghouses tubular SOFCs TSOFCs. The inner layer is a modied lanthanum manganite cathode air electrode. The electrolyte is made of yttria-stabilized zirconia. The anode, or fuel electrode, is made of a nickel-zirconia cermet. Current is extracted from an interconnect material of doped lanthanum chromite. Finally, nickel felt contact padding not shown serves as a means of connecting individual cells to form arrays known as stacks. This design has proven integrity and performance levels for near-term commercialization 1. Despite this technologys present successes, there remain signicant improvements that can be incorporated into operational design. A proven method of energy systems improvement is second law analysis, which a number of investigators have attempted to use with respect to SOFC systems. Various investigations have resulted in systems-level discoveries about SOFC power plants; yet, the second-law characteristics of the cells, themselves, remain an area of needed research. Rosen 2 utilized energy and exergy analyses to compare the cogeneraContributed by the Advanced Energy Systems Division for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received by the AES Division, September 8, 2000; revised manuscript received October 26, 2001. Associate Editor: A. M. Jacobi.

tion efciencies of solid oxide fuel cell systems with other fuel cell systems and electricity generation devices. The work showed the usefulness of exergy analysis in lieu of energy analysis, but did not rigorously address the operating characteristics of a SOFC. Harvey and Richter 3 performed a system study of power plants that included SOFCs. New insights about the plants were conveyed; however, the second law effects within the cell stack were not evaluated since the fuel cell model was a packaged code from another entity. Additionally, the monolithic SOFCs that were highlighted by Harvey and Richter are not as market-ready as are their tubular counterparts. Dunbar et al. 4,5 did highlight TSOFC technology in their second-law studies, using simulations of the then-current cell designs that were based upon empirical data. Gaggioli and Dunbar 6 and Call 7 also focused their second-law studies on TSOFC technology; their work remained theoretical in that they characterized the cell under ideal operating conditions. The next stage of TSOFC second-law studies requires a state-of-the-art model that simulates cell irreversibilities under actual operating conditions. This paper presents second-law evaluations of TSOFCs, wherein the analyses are based on the authors validated model of cell transport phenomena i.e., electrochemical and thermal-uid characterization 8,9. The reader is referred to these papers should she or he desire more information about the fuel cell simulation. Operating point decision variables were varied to understand their impact on performance. Design insights were signicantly enhanced when conventional electrochemical gures-of-merit were supplemented with contemporary engineering thermodynamic measures e.g., exergetic efciency.

Enhancing Fuel Cell Evaluation via Engineering Thermodynamic Second-Law Concepts

Limitations of Conventional Electrochemical Efciencies. Appleby 10 reports the gross real conventional efciency of a fuel cell is the ratio of electric power produced to the extensive heating value of the fuel supply. JUNE 2002, Vol. 124 95

Journal of Energy Resources Technology Copyright 2002 by ASME

Second-law efciencies of power units and systems can measure the ratio of work to reversible work, or the ratio of actual efciency to ideal efciency 14. In fuel cell literature 15, ideal fuel cell efciencies occur when the operating voltage is at its maximum value Nernst potential. Eq. (1 b ) would then become

max

E* u fuelLHVfuel nF

(3)

The corresponding ratio of actual fuel cell efciency to ideal efciency is the voltage efciency

V operate E

(4)

Fig. 1 Isometric view of tubular solid oxide fuel cell

gross,real

iV operate n fuel,inletLHV fuel

(1a)

The authors purposely use the fuel subscript in Eq. (1 a ) since an advantage of SOFCs is their ability to use fuels other than hydrogen e.g., carbon monoxide via shift. The lower heating value is in the denominator, since products are always in existence as gases in the fuel stream of a SOFC. From Faradays law, which is an electrochemical statement of mass conservation, fuel supplied to the fuel cell is proportional to the quotient of current divided by the fuel utilization. n fuel,inlet fuel i nF * u (2)

Voltage efciency is a popular means of analysis 15,16. Note pressure impacts Nernst potential; thus, voltage efciency would be impacted by a change in pressure unlike gross real efciency. Voltage efciency, however, does have drawbacks. Appleby 10 reports arbitrariness in the choice of the Nernst potential used in the denominator. The Nernst potential expressed in the denominator of Eq. 4 may be that corresponding to the anode inlet. Such a value, however, requires a reversible fuel cell i.e., fuel cell with 1 have zero-conversion of reactants. This is because any reactant depletion would be an erroneous proposition that the uniform operating voltage is greater than the Nernst potentials downstream of the inlet. Appleby promotes the usage of Nernst potential at the anode exit. The issue with this denition, however, is that the Nernst potential at the anode exit is only adequate for evaluating polarization losses at that location. Finally, voltage efciency lacks as a second law measure. It only considers the cells direct energy conversion, and not the work potential of heat leaving the cell. This unaccounted-for exergy ow may be used strategically, as was explained. Gaggioli and Dunbar 6 also stress this point. Engineering Thermodynamic Second-Law Evaluation Methods. The voltage efciency measure was shown to have limitations as a second-law measure. A more comprehensive second law efciency is exergetic efciency. Exergetic efciency is here dened as the ratio of power produced divided by the decrease in stream availability i.e., exergy from cell inlet to exit.1 The decrease in stream availability is the maximum producible work potential. iV operate streams,inlet,cell E streams,exit,cell E (5a)

The fuels stoichiometric coefcient represents the overall stoichiometry involved in its electrochemical oxidation e.g., including shift for carbon monoxide. Substituting Eq. 2 into Eq. 1a, the following relationship results:

gross,real

V operate* u fuelLHV fuel nF

(1b)

The only operating variables on the right of the preceding equation are operating voltage and fuel utilization. These variables are not necessarily coupled. It is possible to vary the operating voltage independent of fuel utilization, provided the fuel supply is governed such that fuel utilization remains constant. Likewise, it is possible to vary fuel utilization independent of operating voltage through adjustment of the fuel ow. Further analysis of Eq. (1 b ) reveals deciencies in this efciency measure. There are parameters other than operating voltage and fuel utilization that impact the performance of a fuel cell. As an example, consider operating pressure. Pressure can be increased without impacting the formulation of Eq. (1 b ). Pressure can rise without changing the prescribed operating voltage, with the result being an increase in current due to a corresponding rise in Nernst potentials along the cell. Furthermore, adjustments in fuel supply rates allow for fuel utilization to be independent of pressure. This masked inuence of pressure in Eq. 1 is contradicted by numerous references to pressure as a signicant design parameter 11,12. This oversight of pressure impact is analogous to a shortcoming in the classical analysis of turbomachinery. Two turbine stages may have the same isentropic or adiabatic efciency; yet, the stage at the higher pressure has fewer inefciencies and is a better performer 13. As with isentropic efciency in analyzing turbine stages, the conventional fuel cell efciency may lead to improper conclusions i.e., the unaccounted-for pertinence of operating pressure. Second-law efciencies are an alternative. 96 Vol. 124, JUNE 2002

The exergy availability ows within the inlet and exit streams are calculated by consideration of the physical including ow work and chemical availability terms 17. Kinetic and potential availability terms are neglected. For the given operating conditions, all gases may be presumed ideal. The calculation of the stream availabilities of environmental gases i.e., O2 , N2 , H2 O, CO2 owing about the cell has been simplied in comparison to the conventional approach ref. Appendix. Notice the efuents work potential is considered in the last term of the denominator. This is signicant for fuel cells since the stack exhaust contains unreacted fuel that may be used in ensuing energy conversion units and processes i.e., unused exergy in the efuent is not necessarily lost. This point will also be further explained in a succeeding section. Unlike voltage efciency, exergetic efciency accounts for all irreversibilities. As an example, voltage efciency does not ac1 Heat from the TSOFC exterior is of high quality; however, in the present case study of externally reformed fuel, the thermal energy leaving the cells exterior goes on to be thermal energy dissipation to the ambient. The heat is thus not considered in the numerator of this exergetic efciency. This envelope loss irreversibility is further discussed in the ensuing section.

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Fig. 2 Heat transfer within the cell

count for the irreversibility associated with sensibly heating airow inside the cell. This is especially important when one considers the signicant difference between typical inlet air temperatures and that of the SOFC 9. Additionally, there is no variance in the calculation of maximum reversible work, as was revealed of voltage efciency i.e., the denominator of Eq. (5 a ) is not arbitrarily dened as discussed of the Nernst value used in Eq. 4. Categorizing Availability Destruction via the Distribution of Irreversibilities. Accounting for availability along a TSOFC allows for the tracking of availability destruction. Availability is destroyed by a variety of means within the TSOFC. These include heat transfer, mass transfer, and spontaneous electrochemical reactions. A means of establishing the distribution of inefciencies is the specication of various entropy generation phenomena i.e., categorization of irreversibilities. The Gouy-Stodola theorem states the direct proportionality between irreversibility and entropy generation. total T o S gen,total I (6)

electrochemical T o I

i V total T cell

(8b)

Since the irreversibilities represent lost work from the ideal case, the following substitution may be made into Eq. (5 a ): iV operate total iV operate I (5b)

The rst term on the right of Eq. (8 a ) is a statement of the electrochemical power not produced, due to the voltage drop from theoretical Nernst potential to actual operating voltage. This is due to polarization and internal resistances 8. Thermal energy, in the amount of I V total , is instead generated. The second term considers the quality of the resulting heat. Ratkje and Moller-Holst 18 performed extensive second-law analyses of SOFC unit cells, wherein they did not account for the thermal exergy of the highquality heat rejected from these cells i.e., in their maximum work evaluations. Equation (8 b ) is a simplied expression. Notice that a distinctive means of measuring electrochemical entropy generation is presented. Considering Eq. 7, electrochemical entropy generation is the quotient factor in Eq. (8 b ). This is a novel instance of electrochemical entropy generation being calculated from directly measurable quantities: cell temperature, current, Nernst potential2 and operating voltage. No thermophysical property data or correlation is needed. Dunbar and Gaggioli 21 formulated a similar entropy generation term within their second-law analysis of solid oxide fuel cells, wherein they performed an indepth subcategorization of the sources of entropy generation that contribute to electrochemical irreversibility. Finally note that, in the calculation of exergetic efciency, electrochemical irreversibility was calculated via electrochemical I

Quantifying the different sources of entropy generation allows for more insight into process inefciencies. Electrochemical Irreversibility. Using the Gouy-Stodola theorem to quantify electrochemical irreversibility electrochemical T o S gen,electrochemical I (7)

slices

iT

To
cell

Eslice V op

(9)

Irreversibility is the loss of producible power; therefore, electrochemical irreversibility takes the following form: electrochemical i V total i V total I

The slices referred to are in conjunction with the axial discretization used in numerically simulating the cell 8. This formulation resolves the issue of establishing a singular, representative Nernst potential in second-law evaluations i.e., a challenge in
2 Nernst potential is approximated as the open circuit voltage due to the large exchange current density that occurs at the high operating temperatures of TSOFCs nominally 1000C. This approximation has been conrmed by Minh and Takahashi 19 and Maskalick 20, among others.

To 1 T cell

(8a)

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Table 1 Baseline operating conditions for cell stack

The power conditioner efciency is here dened as the fraction of direct current d-c power that becomes alternating current a-c power. Envelope Loss Irreversibility. The high temperature fuel cell stack has envelope losses to the environment. Considering that the high-temperature cell is the source of heat, power could be produced by the heat reference the rst footnote heat,env.loss 1 Powerreversible,heat,env.loss Q

To T cell

(12a)

Realizing that no work is produced, Eq. (12 a ) represents lost power, and thus irreversibility env.loss Q heat,env.loss 1 I using the conventional voltage efciency. Gaggioli and Dunbar 6 offer a similar commentary on effectively considering Nernst distribution along the cell when performing second law analyses. Heat Transfer Irreversibility within the Cell. Given the scenario of external fuel processing, cogenerated thermal energy has to be convected to the oxidant stream 9. Figure 2 shows thermal transport within a fuel cell. Air is supplied to the cell by means of an alumina supply pipe. Upon exiting the air supply pipe into the closed end of the cell, the air reverses direction and serves as the oxidant stream. Exterior to the cell, fuel ows in the same direction as the oxidant stream. Electrochemical phenomena between the electrodes generate thermal energy in addition to electricity. An electrochemical model was developed that is accurate to within 35% of experimental values 8. The establishment of an accurate electrochemical model enabled the construction of an accurate heat transfer model 9, since it is primarily the byproduct thermal energy of electrochemical phenomena that drives thermal transport. Heat transfer irreversibility stems from thermal transport across signicant temperature differences. Figure 2 shows the passages in which heat is convected to the air. Fluid frictional irreversibility was found to be negligible in comparison to heat transfer irreversibility 22. The heat transfer entropy production within the cell can thus be quantied via a steady-state entropy balance on the control volume whose surfaces are those of the air passages. heat,in-cell T o S gen,heat I gen,heat,in-cell S out S in S out m S oxidants oxidantexit in S air Q T boundaries m airs airinlet,ASP (10) (10a) (10b) (10c)

T0 T cell

(12b)

Fuel Stream Irreversibilities. The current focus on external reformation resulted in signicantly reduced irreversibilities within the fuel stream as it passes through the cell stack. In this study, fuel stream irreversibilities were neglected. Understanding these various inefciencies that occur with regard to SOFCs aided the ensuing design analysis.

Analyzing the Impact of Process Decision Variables on Cell Performance

Process settings were varied to understand their respective impacts on the quality of cell operation. Additionally, comparisons were made between traditional, electrochemical efciencies and the contemporary, second law concepts discussed. The decision variables were stack pressure, air stoichiometric number i.e., inverse equivalence ratio, operating voltage, and stack fuel utilization. The baseline operating conditions are stated in Table 1. The settings are a compilation of typical external fuel processing values reported by SiemensWestinghouse and the Department of Energy 23,11. In each of the following discussions, independent variables besides the highlighted decision variable are parameters with the values given in Table 1. Pressure. Figure 3 illustrates the functional dependence of efciencies on operating pressure. The voltage and exergetic efciencies Eqs. 4 and 5, respectively are signicantly higher than the gross real efciency Eq. 1. Second-law efciencies are typically greater, because their denominators pertain to the maximum work possible; maximum work is usually smaller than extensive heating value as in this case where hydrogen-rich syn gas is fed to the cells. Exergetic efciency is greater than voltage efciency. This is primarily because the denominator of exergetic efciency accounts for the work potential of efuent exiting the cell i.e., the difference expression in the exergetic efciency denominator. Gross real efciency shows no dependence on operating pressure. This lack of functionality was discussed earlier. Voltage and exergetic efciencies, however, decline. The operating voltage remains xed while pressure, and thus average Nernst potential, increases.3 Polarization terms then increase due to larger differences between theoretical Nernst and actual operating potentials along the cells; thus, the quality of cell performance suffers. The decreasing impact of pressure is due to the logarithmic dependence of Nernst potential on pressure. Stoichiometric Number. The stoichiometric number efciency proles further attest to the value of exergetic efciency in analyzing fuel cells. Figure 4 contains the efciency proles as functions of stoichiometric number. Gross real cell efciency has no dependence on stoichiometric number since neither prescribed operating voltage nor fuel utilization is a function of stoichiometric number. Voltage efciency has a slight decrease with
3 In the given analysis, the arithmetic average Nernst potential as determined by the Nernst values at the cell slices 8 was used to calculate voltage efciency.

The boundary temperatures at all points of heat transfer to the air i.e., in the air supply pipe and in the annular region are near the cell temperature of 1000C; thus, the large number of transfer units i.e., NTU within the air supply pipe causes the oxidant stream to routinely come into thermal equilibrium with the cell 9. The following approximation is thus made for substitution in Eq. (10c ) . air Q m air c p ,avg T cell T air,inlet T boundaries T cell (10d)

Power Conditioning Irreversibility. Power conditioning equipment often accompany fuel cell technology. The fuel cells produce direct current electricity, and often the direct current must be converted into alternating current of some prescribed frequency. This additional energy conversion step results in additional losses. power,conditioning 1 conditioner Powercell I 98 Vol. 124, JUNE 2002 (11)

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Fig. 5 Functional dependence of major irreversibilities on stoichiometric number

Fig. 3 a: Functional dependence of gross real efciency on operating pressure b: Functional dependence of second-law efciencies on operating pressure

increasing stoichiometric number. Although larger stoichiometric numbers mean greater partial pressures of oxygen along the cell, Nernst potential primarily depends upon the fuel stream constituents. Conning ones analysis to these conventional measures would lead to the conclusion that stoichiometric number has little effect on cell performance. Exergetic efciency proves otherwise. Notice the increase in exergetic efciency as stoichiometric number increases, especially at lower values. This stems from the decrease in thermal irreversibilities as stoichiometric number increases. Figure 5 proles the dominant irreversibilities i.e., sensible heating of air, electrochemistry, power conditioning as functions

of stoichiometric number. Fuel stream irreversibilities were already explained to be negligible within the present case of an externally reformed fuel stream. Additionally, the small envelope loss coefcient i.e., 2% resulted in small envelope irreversibilities the maximum value for this irreversibility in the given analysis was 4.375 W. Envelope loss irreversibility remained small throughout the entire domain of simulations; however, the expression of Eqs. (12 b ) remains important since higher envelope loss coefcients may be realized in future validations. As with the gross real and voltage efciencies, the commutation and electrochemical irreversibilities are solely functions of lost electrochemical power generation. As explained in the previous paragraph, stoichiometric number has a small effect on electrochemical power generation. Stoichiometric number elevation, however, signicantly lowers thermal irreversibilities. It may seem counterintuitive that greater stoichiometric numbers heighten stack performance, since excess air often degrades thermal system efciency 17. The resolution, however, lies in considering the dependency of inlet air temperature on stoichiometric number. Greater stoichiometric numbers correspond to greater air mass ows. There is thus an increase in the inlet air temperature so that the cells do not cool below the design temperature. This increase in inlet air temperature is shown in Fig. 6 9. Cell stack heat transfer to the oxidant stream thus occurs across smaller temperature differences. The result is smaller entropy generation. Again referencing Fig. 5, thermal irreversibility begins as the most dominant form of irreversibility; however, as stoichiometric number increases, it becomes the least of the major irreversibilities. The exergetic efciency prole is the only index-of-performance that reveals the enhanced operation within the cell stack resulting from higher stoichiometric numbers. Notice the exergetic ef-

Fig. 4 Functional dependence of efciencies on stoichiometric number

Fig. 6 Variation of stack inlet air temperature as a function of air stoichiometric number

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Fig. 7 Functional dependence of efciencies on operating voltage

Fig. 9 Functional dependence of efciencies on fuel utilization

ciency prole in Fig. 4 attens at higher stoichiometric numbers, reecting the asymptotic decrease of thermal irreversibility in Fig. 5. There are, however, added system requirements when stoichiometric number is raised. Larger uid-handling equipment is required, and there is a greater air preheat load i.e., more is required of a recuperator/ air preheat preceding the cell stack. Operating Voltage. The operating voltage efciency proles are distinguished by the uniform slopes of the conventional cell efciencies and the crossing of the second law efciencies at elevated voltages. This is shown in Fig. 7. The direct proportionality of the gross real and voltage efciencies to operating voltage is evident by inspection of Eqs. 1 and 4. Figure 8 illustrates how irreversibilities converge towards zero as operating voltage increases. As operating voltage increases, current goes to zero i.e., the potential force for charge transport vanishes as operating voltage nears theoretical Nernst potential. Since current is the primary transport phenomena e.g., it drives heat transfer, irreversibilities also go to zero. Concomitant to the disappearance of irreversibilities, reversible operation becomes more imminent albeit power generation goes to zero. This is the reason for the exceptionally high second-law efciencies of Fig. 7. The crossing of the second-law efciencies in Fig. 7 motivates another comparison and contrast between voltage and exergetic efciencies. The voltage efciency plot shows a uniform or near-uniform approach to unity. In contrast, the exergetic efciency has a decreasing approach to unity. Exergetic efciency shows that an increase in operating voltage does not foster a uniform approach to ideal operation. Note, this is more representative of the nonuni-

form irreversibility proles shown in Fig. 8. Again, the exergetic efciency is proven to be a more insightful index-of-performance than conventional electrochemical efciencies. Fuel Utilization. Fuel cells are not operated at 100% fuel consumption due to reactant depletion issues i.e., severe concentration polarization causing decreased efciency, possible electrode contamination, etc.. The major thrust in fuel cell development has been to maximize cell stack fuel utilization, however, so that reactants are not wasted. Interestingly, exergetic efciency did not indicate a negative effect at lower fuel utilizations. Figure 9 is a graph of cell efciencies as functions of fuel utilization. Gross real cell efciency increases with fuel utilization, due to its linear dependence on the parameter ref. Eq. (1 b ) . Voltage efciency increases, because, as fuel utilization increases, the average Nernst potential will lessen due to reactant depletion ref. Eq. 4. These conventional measures thus support the notion that cell stack fuel utilization should be maximized, given an invariant operating voltage. Exergetic efciency, showing an opposite trend, has a slight decrease (a percentage point) across the domain. Figure 10 illustrates the ratios of dominant stack irreversibilities-to-cell power as functions of fuel utilization. The commutation ratio is unaffected, since power conditioner efciency is unaffected by fuel utilization. As expected, the electrochemical irreversibility ratio decreases with fuel utilization. A given transport phenomenon in this case, current causes entropy generation in proportion to its driving force in this case, the difference between Nernst potential and operating voltage. The dif-

Fig. 8 Functional dependence of major irreversibilities on operating voltage

Fig. 10 Ratios of preeminent irreversibilities to stack power production

100 Vol. 124, JUNE 2002

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V operate Eend-cell

(4a)

Fig. 11 Impact of fuel utilization on stack inlet air temperature

ferences between stream Nernst potentials and operating voltage decrease with fuel utilization, since there is greater reactant depletion 8. This trend relates to the electrochemical efciency increases seen in Fig. 9. Exergetic efciencys additional consideration of thermal irreversibility is the source of contrast. Notice the thermal irreversibility ratio of Fig. 10 increases with fuel utilization. Higher fuel utilizations correlate to decreases in inlet air temperatures, due to greater thermal energy generation and heat transfer per unit mass of airow 9. This trend is shown in Fig. 11. A result is heat transfer across larger temperature differences, at higher fuel utilizations. Again, a given transport phenomenon now heat causes entropy generation in proportion to its driving force temperature difference. This is the reason for the increase in the thermal irreversibility ratio of Fig. 10. The total irreversibility ratio thus has an increase its rise is buffered, however, due to the competing electrochemical trends. As a corollary, exergetic efciency has the slight decline noted in Fig. 9. Again the consideration of thermal irreversibility within exergetic efciency is a major reason for this index-of-performances distinction. The realization that lowering cell stack fuel utilization is not necessarily detrimental may be further appreciated by considering that unoxidized fuel leaving the cell stack need not be wasted. Fuel cell stacks may be set up in series such that fuel not utilized in a given stack, under analysis, may be used in a following one. Unreacted fuel may also be used in advanced recirculation loops, or to re fuel processing sections and bottoming heat engines. A program of high priority to the United States National Energy Technology Laboratory formerly Federal Energy Technology Center is the incorporation of solid state fuel cells as topping units in hybrid fuel cell/gas turbine power systems 24. In such cases the balance-of-plant usage of unoxidized fuel should be considered in the evaluation of system efciency. The dened exergetic efciency does not penalize the cell stack for passing along exergy that can be used elsewhere again reference the exergy ow difference in the denominator of Eq. (5 a ) . The conventional efciency measures do not include such insight. This concludes some counterintuitive ndings regarding cell stack fuel utilization. Lower fuel utilization can enable greater power generation 8 without degrading the stack performance. Some nal points are now made in comparison of the different efciencies, as far as fuel utilization is concerned. The conventional, electrochemical attempt at a second law efciency was already shown to have an arbitrary aspect, since there is no standard Nernst potential value used in the denominator ref. Eq. 4. There is another point of ambiguity that may arise, depending on fuel utilization. Assume the popular yet nonstandard choice of end-cell Nernst potential is used within the denominator of the voltage efciency measure Journal of Energy Resources Technology

Now, suppose the reactant streams have large molar ow rates, such that fuel utilization is small and the end-cell Nernst potential is nearly the inlet value. Additionally, assume a sizable value for the operating voltage is selected such that its value is near the supplied reactants Nernst potential. A large voltage efciency will result. This is shown in the following Fig. 12a. Now, consider a scenario where the operating voltage is signicantly lower than the inlet Nernst potential, and the reactant streams are not composed of large molar ows. Fuel utilization is large enough that the end-cell Nernst potential is near the operating voltage. The result may again be a high voltage efciency, possibly near that of the former case. This is shown in the following Fig. 12b. Obviously, however, the rst scenario with operating voltage consistently near the streams Nernst potentials, should have a better second law performance rating because smaller thermodynamic driving forces are maintained. This is another example of the need for supplemental indices-of-performance such as exergetic efciency.

Conclusions
The second-law concepts of availability or exergy, irreversibility, and exergetic efciency enhance the analysis and process design of fuel cells. There are numerous causes of nonideal fuel cell operation electrochemical losses, heat transfer across nite temperature differences, etc.. These sources of inefciency can be isolated for analysis via a study of irreversibilities. Unlike the conventional indices-of-performance i.e., gross real and voltage efciencies, exergetic efciency accounts for thermal exergy and thermal irreversibilities. These considerations are especially important when considering higher temperature cells, such as solid oxide fuel cells. Finally, exergetic efciency can account for the value of unreacted fuel leaving the fuel cell, unlike the conventionally used efciencies. A successfully modeled solid oxide fuel cell was analyzed with the second law concepts. The decision variables varied were pressure, air stoichiometric number inverse equivalence ratio, operating voltage and fuel utilization. Operating pressure did not affect gross real cell efciency. Voltage and exergetic efciencies were inuenced. They decreased in a manner reective of the logarithmic dependence of Nernst potential on pressure. The gross real and voltage efciencies were independent of stoichiometric number. These measures do not consider the decrease in heat transfer irreversibility that accompanies increased airow; yet, the heat transfer irreversibility is a large source of inefciency. Exergetic efciency does increase with stoichiometric number. The increase drops off considerably, however, at higher values. An increase in operating voltage caused a nearly uniform increase in gross real and voltage efciencies. This trend is particularly noteworthy when considering voltage efciency, because it predicted a nearly constant approach to 100% efciency as the prescribed voltage was increased. Exergetic efciency had an asymptotic approach to ideal operation; this better agreed with the asymptotic decrease in irreversibilities as operating voltage was elevated. Finally, exergetic efciency was the only efciency measure that did not penalize the rating of a cells performance based upon non-usage of exergy which could be used elsewhere. This insight, coupled with exergetic efciencys inclusion of thermal irreversibilities, led to a stability of the measure with fuel utilization increase. This was contrary to the increases of the conventional efciency measures, at higher fuel utilizations. Exergetic efciency was thus shown to be a worthwhile index-of- performance to use in fuel cell design. It supplements the popular electrochemical efciency measures. JUNE 2002, Vol. 124 101

Fig. 12 a Large voltage efciency due to consistent proximity of operating voltage to Nernst potentials along cells. b Large voltage efciency due to proximity of operating voltage to Nernst potential at the end of the cell.

Throughout the preceding body of this publication the premise has been that the cells receive steam-hydrocarbon reformate or syn gas formed via external reformation. This means fuel processing occurred in a component preceding the cell stack. There are benets to using this mode of fuel processing, and other analyses have included the assumption of external reformation 25. The prevalent development, however, is to take advantage of the high operating temperatures of SOFCs for internal reformation. This involves fuel being processed within the cell stack. Note that the primary method of internal reformation is indirect internal reformation IIR; hydrocarbons are not reformed over the anode, but in an adjacent compartment 22. This mitigates coking det102 Vol. 124, JUNE 2002

rimental deposits of carbon and cold spots on the cell. The fuel stream that ows over the fuel cell is then a reformate mixture of the same compounds referenced in this paper. Future design studies will incorporate the added chemistry and transport phenomena of internal reformation. Experimental data will be used to validate the IIR model, as was done with the currently used model. Lastly, capital cost is the primary hindrance to the usage of fuel cell technology in the marketplace. Thermoeconomic or exergoeconomic methods, which build upon the exergy analyses of the present article, will thus be included within future investigations as well. Transactions of the ASME

Nomenclature
cp E E G h i I LHV m j n i nF pk q,Q R Ru s S T u V specic heat at constant pressure (J/kg* K) exergy ow rate W Nernst potential J/C Gibbs free energy J/rxn molar specic enthalpy J/mol current C/s irreversibility rate W lower heating value J mass ow rate of j kg/s molar ow rate of constituent i mol/s charge transferred per reaction C partial pressure of gas k atm heat transfer, generation W resistance ohms universal gas constant (J/mol* K) molar specic entropy (J/mol* K) entropy rate W/K absolute temperature K cell stack fuel utilization voltage J/C change in quantity emissivity, exergetic efciency efciency stoichiometric coefcient availability J/mol

References
1 Veyo, S. V., 1998, Tubular SOFC Power System Operational Experience, Abstracts of the 1998 Fuel Cells Seminar, Palm Springs, pp. 457-460. 2 Rosen, M. A., 1990, Comparison Based on Energy and Exergy Analyses of the Potential Cogeneration Efciencies for Fuel Cells and Other Electricity Generation Devices, Int. J. Hydrogen Energy, 15, No. 4, pp. 267274. 3 Harvey, S. P., and Richter, H. J., 1994, Gas Turbine Cycles With Solid Oxide Fuel Cells; Part II: A Detailed Study of a Gas Turbine Cycle With an Integrated Internal Reforming Solid Oxide Fuel Cell Technology, ASME J. Energy Resour. Technol., 116, pp. 312318. 4 Dunbar, W. R., Lior, N., and Gaggioli, R. A., 1991, Combining Fuel Cells with Fuel-Fired Power Plants for Improved Exergy Efciency, Energy Oxford, 16, No. 10, pp. 12591274. 5 Dunbar, W. R., Lior, N., and Gaggioli, R. A., 1993, The Effect of the FuelCell Unit Size on the Efciency of a Fuel-Cell-Topped Rankine Power Cycle, ASME J. Energy Resour. Technol., 115, pp. 105107. 6 Gaggioli, R. A., and Dunbar, W. R., 1993, Emf, Maximum Power and Efciency of Fuel Cells, ASME J. Energy Resour. Technol., 115, pp. 100104. 7 Call, F. W., 1998, DispersionAn Entropy Generator of Diffusion, ASME J. Energy Resour. Technol., 120, pp. 149152. 8 Haynes, C. L., and Wepfera, W. J., Design for Power of a CommercialGrade Tubular Solid Oxide Fuel Cell, Energy Convers. Manage., 41, pp. 1123-1139; Erratum, 41, 20632067. 9 Haynes, C. L., and Wepferb, W. J., 2000, Characterizing Heat Transfer within a Commercial-Grade Tubular Solid Oxide Fuel Cell for Enhanced Thermal Management, Int. J. Hydrogen Energy, accepted for publication. 10 Appleby, A. J., 1993, Characteristics of Fuel Cell Systems, Fuel Cell Systems, L. J. M. J. Blomen and M. N. Mugerwa, eds., Plenum Press, New York, NY, pp. 157200. 11 Hirschenhofer, J. H., Stauffer, D. B., and Engelman, R. R., 1994, Fuel Cells, A Handbook Revision 3, DOE/METC-94/1006, United States Department of Energy, Morgantown, VA. 12 Mugerwa, M. N., and Blomen, L. J. M. J., 1993, System Design and Optimization, Fuel Cell Systems, L. J. M. J. Blomen and M. N. Mugerwa, eds., Plenum Press, New York, NY, pp. 216 219. 13 Jones, J. B., and Dugan, R. E., 1996, Engineering Thermodynamics, PrenticeHall, Englewood Cliffs, NJ, p. 729. 14 Moran, M. J., and Shapiro, H. N., 1992, Fundamentals of Engineering Thermodynamics, Second Edition, John Wiley & Sons, New York, NY, pp. 289 296. 15 Barendrecht, E., 1993, Electrochemistry of Fuel Cells, Fuel Cell Systems, L. J. M. J. Blomen and M. N. Mugerwa, eds., Plenum Press, New York, NY, p. 76. 16 Prentice, G., 1991, Electrochemical Engineering Principles, Prentice-Hall, Englewood Cliffs, NJ, p. 14. 17 Bejan, A., Tsatsaronis, G., and Moran, M., 1996, Thermal Design and Optimization, John Wiley & Sons, New York, NY. 18 Ratjke, S. K., and Moller-Holst, S., 1993, Exergy Efciency and Local Heat Production in Solid Oxide Fuel Cells, Electrochim. Acta, 38, No. 2/3, pp. 447 453. 19 Minh, T. Q., and Takahashi, T., 1995, Science and Technology of Ceramic Fuel Cells, Elsevier, Amsterdam, Holland. pp. 2223. 20 Maskalick, N. J., 1989, Design and Performance of Tubular Solid Oxide Fuel Cells, Proc. First International Symposium on Solid Oxide Fuel Cells, Hollywood, FL. 21 Dunbar, W. R., and Gaggioli, R. A., 1990, Computer Simulation of Solid Electrolyte Fuel Cells, ASME J. Energy Resour. Technol., 112, pp. 114 123. 22 Haynes, C. L., 1999, Simulation of Tubular Solid Oxide Fuel Cell Behavior for Integration into Gas Turbine Cycles, Ph.D. dissertation, Georgia Institute of Technology. 23 George, R. A., and Bessette, N. F., 1998, Reducing the Manufacturing Cost of Tubular SOFC Technology, J. Power Sources, 71, pp. 131137. 24 Federal Energy Technology Center, 1999, Solid Oxide Fuel Cell Project: Generating Tomorrows Electricity Cleanly, Project Facts: Department of Energy, Ofce of Fossil Energy, Federal Energy Technology Center, Federal Energy Technology Center, Morgantown, VA. 25 Demin, A. K., Alderucci, V., Ielo, I., Fadeev, G. I., Maggio, G., Giordano, N., and Antonucci, V., 1992, Thermodynamic Analysis of Methane Fueled Solid Oxide Fuel Cell System, Int. J. Hydrogen Energy, 17, No. 6, pp. 451 458.

Appendix
Simplied Availability Terms for Atmospheric Gases Within SOFC Stack. Availability accounting of atmospheric gases is important in the second law analysis of solid oxide fuel cells. Air is the oxidant. Carbon dioxide is present within the fuel stream. Finally, steam is the product of oxidation and is required for shift. These atmospheric gases have no afnity for reaction with the environment; thus, they only have a thermomechanical here including diffusional availability. They reach their unrestricted dead state at atmospheric temperature and their atmospheric partial pressure. Their respective availabilities can thus be simplied. atm,gas h i T h i T o T o s i T , p i s i T o , p i e (13) This equation is particularly benecial for steam calculations, since property differences may be calculated using ideal gas relations. The conventional method would require involved property difference calculations between ideal gas steam as it exists along the cell or in the atmosphere and subcooled water at reference conditions ( T o , p o ). Finally, the conventional method involves looking up tabular values for chemical availability; the proposed method of 13 eliminates errors that may result from using inconsistent tables. Inconsistent tables are due to the variance in models of the thermodynamic reference environment a.k.a. exergy reference environment 17.

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Comas Lamar Haynes is a faculty member at the Georgia Tech Center for Innovative Fuel Cell and Battery Technologies. His research includes modeling fuel cell behavior, thermal management of fuel cells, second law analyses of fuel cells, and the thermodynamic optimization of hybrid fuel cell/ heat engine cycles. Example investigations include using heat exchanger analogies in advanced fuel cells designs, cost-effective thermal management of low and high temperature fuel cells via optimal electroactive area allocation, and fuel cells system integration and optimization for advanced vehicles. He also develops fuel cells systems curricula for public and college course and experimental laboratories.

William J. Wepfer is Professor and Associate Chair of Graduate Studies in the George W. Woodruff School of Mechanical Engineering at Georgia Tech. He received his BSME from Marquette University, the MSME from Stanford and the Ph.D. from Wisconsin. His research focuses on thermal processing (heat and mass transfer) of textile composites, system analysis of advanced solid oxide fuel cell systems, and the design and optimization of energy systems. Dr. Wepfer is author of over 80 papers. Dr. Wepfer is a Fellow member of ASME and ASHRAE. Dr. Wepfer has administrative responsibility for the Woodruff Schools graduate programs that includes a signicant distance learning component as well as an international component at Georgia Tech Lorraine in France.

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