Mench M.M. Fuel Cell Engines

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480 Experimental Diagnostics and Diagnosis

PROBLEMS

9.1 What is meant by ohmic and nonohmic resistance con-

tributions?

9.2 Describe the basic physical principle on which EIS is

based.

9.3 A cyclic voltammogram is obtained by varying the

potential on an electrode surface and measuring the result-

ing current. Could the process be changed to measure the

voltage change at a constant current? Would this have any

advantages? Hint: Read ref. [4].

9.4 What is the physical meaning of the proportionality

constant used in determining the ECSA? Would the value

of 210 µC/cm

for platinum be good for a nickel electrode

in a SOFC? Why or why not?

9.5 How would you measure or obtain the proportionality

constant used in determining the ECSA?

9.6 What are some of the degradation effects listed in Chap-

ter 6 for PEFCs that would result in loss of ECSA for PE-

FCs?

9.7 Would a ﬂooded or dried PEFC electrode affect the

EIS results? Qualitatively sketch a EIS Nyquist plot for a

normal, dried, and ﬂooded PEFC electrode situation.

9.8 What would the effect of electrolyte contamination and

degradation of an AFC be on the expected Nyquist EIS

plot?

9.9 In a PEFC, the high-current-density performance can

be low as a result of ﬂooding the electrode or anode dryout.

How could you experimentally delineate the difference?

9.10 Does the use of a dynamic hydrogen electrode become

more or less appropriate at high current density? Why or

why not?

9.11 Qualitatively sketch a current-interrupt voltage versus

time response for a solid oxide, direct methanol, and poly-

mer electrolyte fuel cell system. Remember to think about

what is limiting each fuel cell under normal operation.

9.12 Why does the Tafel slope in Figure 9.12 deviate from

linearity? Would a higher pressure cathode feed delay the

departure?

9.13 Discuss some of the limitations and advantages of

EIS. What parameters can you get from its use?

9.14 Would any of the current distribution methods dis-

cussed be applicaple in a full-size stack?

9.15 Can you calculate the electrolyte temperature from a

temperature probe in the bipolar plate of a PEFC or would

a sensor have to be directly in the electrolyte? What sort

of temperature difference between the bipolar plate and the

catalyst layer do you anticipate at 1 A/cm

9.16 What practical experimental concerns would you have

if you are replacing a portion of the bipolar plate in a PEFC

with a plexiglass window to observe liquid water formation

and motion?

9.17 Assume that you have a method in your laboratory for

perfect species mole fraction measurement at selected lo-

cations along a single channel in a PEFC. Experimentally,

describe how you could measure the diffusivity of water

in the electrolyte/catalyst layer/DM membrane electrode

assembly. Hint: Consider developing an along-the-channel

model to use with your experimental data.

9.18 In a PEFC, there are often phase change processes

such as vaporization, condensation, and freezing or melting.

If you were using an infrared device to observe the instanta-

neous temperature distribution in a PEFC, what would you

expect to see during the various phase change events, an

increase or decrease in the local temperature? Would the

phase change affect the overall energy balance in the fuel

cell?

9.19 Is a technique for current distribution measurement

necessary with the SOFC? What can be used instead of a

direct distributed current measurement?

9.20 Would the ohmic resistance measured with the HFR

technique be over- or underestimated if the frequency cho-

sen was not sufﬁciently high?

9.21 One potential way to measure the liquid water accu-

mulation and depletion in a PEFC is by weighing the cell

during operation. What is the practical limitation with this

approach? Could it work?

9.22 In an AFC, carbon dioxide impurity can degrade the

performance of the electrolyte over time. How can the effect

of CO

impurity on the electrolyte be precisely quantiﬁed

and modeled?

9.23 In a MCFC, it is believed that the current-collecting

grid structure corrosion is causing performance degradation

over time. How could this be experimentally conﬁrmed or

refuted?

9.24 How could you measure the loss of electrolyte from a

PAFC system due to vaporization?

c09 JWPR067-Mench December 16, 2007 15:15 Char Count=

References 481

9.25 In a PAFC system you are operating, it is suspected

that the catalyst on an electrode is somehow dissolving at

high potential conditions >0.8 V. How would you propose

to experimentally conﬁrm or refute and model this occur-

rence?

9.26 Deduce a one-dimensional model to explain how the

species proﬁle can be predicted from knowledge of the cur-

rent density in an SOFC. Could the approach be used to

deduce the current distribution if the species proﬁles are

known?

9.27 Deduce a one-dimensional model to explain how the

species proﬁle can be predicted from knowledge of the cur-

rent density in a PEFC. What are the main complicating

uncertainties in this model? Could the approach be used to

deduce the current distribution if the species proﬁles are

known?

Open-Ended Problems

9.28 Go online and ﬁnd a few references that discuss the

use of a reference electrode for a fuel cell or the develop-

ment of a reference electrode for fuel cell use. Explain why

this has been difﬁcult to apply in practice.

9.29 It has long been a challenge to observe the liquid wa-

ter accumulation and motion within the catalyst layer of a

PEFC. Are there any experimental techniques you can think

of or that have been developed to accomplish this?

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of Polymer Electrolyte Fuel Cells,” in Proceedings of the 206th Meeting of the ECS, Proton

Conducting Membrane Fuel Cells, Vol. 4, M. Murthy Ed., Honolulu, HI, pp. 551–564, 2004.

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Thesis, NTN University, Trondheim, Norway, 2002.

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Electrolyte Fuel Cell,” Electrochem. Acta, Vol. 49, pp. 1069–1077, 2004.

34. D. J. Burford, T. W. Davis, and M. M. Mench, “In Situ Temperature Distribution Measurements in

an Operating Polymer Electrolyte Fuel Cell,” in Proceedings of the 2003 International Mechani-

cal Engineering Congress and Exposition (IMECE), Symposium, Paper No. 42393, Washington,

DC, November 2003.

35. D. J. Burford, T. W. Davis, and M. M. Mench, “Heat Transport and Temperature Distribution

in PEFCs,” in Proceedings of the 2004 International Mechanical Engineering Congress and

Exposition (IMECE), IMECEC 2004–59497, Anaheim, CA, November 2004.

36. S. He, M. M. Mench, and S. Tadigadapa, “Thin Film Temperature Sensor for Real-Time Mea-

surement of Electrolyte Temperature in a Polymer Electrolyte Fuel Cell,” Sensors and Actuators

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37. K. T

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38. X. G. Yang, F. Y. Zhang, A. L. Lubawy, and C. Y. Wang, “Visualization of Liquid Water Transport

in a PEFC,” Electrochem. Solid State Lett., Vol. 7, No. 11, pp. A408–A411, 2004.

39. H. S. Kim, T. H. Ha, S. J. Park, K. Min, and M. Kim, “Visualization Study of Cathode Flooding

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40. E. C. Kumbur, K. V. Sharp, and M. M. Mench, “Liquid Droplet Behavior and Instability in

a Polymer Electrolyte Fuel Cell Flow Channel,” J. Power Sources, Vol. 161, pp. 335–345,

2006.

41. J. J. Kowal, A. Turhan, K. Heller, J. S. Brenizer, and M. M. Mench, “Liquid Water Storage,

Distribution, and Removal from Diffusion Media in PEFCs,” J. Electrochem. Soc., Vol. 153, pp.

A1971–A1978, 2006.

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Investigation of Two-Phase Flow Patterns in Flow Fields of PEFC’s using Neutron Radiography,”

Fuel Cells, Vol. 2, pp. 92–98, 2002.

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129, pp. 238–245, 2005.

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47. K. Heller, L. Shi, J. Brenizer, and M. M. Mench, “Error Analysis of Water Quantiﬁcation Using

Neutron Imaging,” World Conference on Neutron Radiography (WCNR-8), NIST, Gaithersburg,

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(PIV) for Application to the Design of Fuel Cell Reactant Flow Channels,” J. Power Sources,

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app JWPR067-Mench December 13, 2007 17:33 Char Count=

Appendix

Some selected journals which publish fuel cell articles:

Applied Catalysis A- General

Catalysis Today

Chemical Reviews

Electrochimica Acta

Electrochemical and Solid State Letters

Electrochemistry

Electrochemistry Communications

Fuel Cells

International Journal of Heat and Mass Transfer

International Journal of Hydrogen Energy

Journal of Applied Electrochemistry

Journal of Catalysts

Journal of Electroanalytical Chemistry

Journal of Fuel Cell Science and Technology

Journal of New Materials for Electrochemical Systems

Journal of Physical Chemistry B

Journal of Power Sources

Journal of the American Ceramic Society

Journal of the Electrochemical Society

Journal of Materials Science

Journal of Membrane Science

Solid State Ionics

Some selected general interest Websites:

http://www.fuelcells.org/ Regularly updated fuel cell information site

http://www.cafcp.org/ California fuel cell vehicle partnership site

http://www.sae.org/fuelcells/fuelcells.htm American Society of Automotive Engi-

neers Fuel Cell site

http://www.hfcletter.com/ Hydrogen and fuel cell letter

http://www.fuelcelltoday.com/ Regularly updated fuel cell information site

485

Fuel Cell Engines

Matthew M. Mench

app JWPR067-Mench December 13, 2007 17:33 Char Count=

486 Appendix

http://www.fuelcellsworks.com/ Regularly updated fuel cell information site

http://www.fuelcelleurope.org/ European fuel cell information site

http://www.eere.energy.gov/hydrogenandfuelcells/ U.S. Department of Energy, En-

ergy Efﬁciency and Renewables program information site

http://www.fossil.energy.gov/programs/powersystems/fuelcells/ U.S. Department of

Energy, fuel cells program information site

http://www.hydrogenassociation.org/general/fuelingSearch.asp National Hydrogen

association site

http://webbook.nist.gov/chemistry/ National Institute of Standards and Technology

site for thermoﬂuidic property data.

http://www.convertit.com/ Units conversion calculator

Table A . 1 Critical Properties of Selected Fuel Cell Gases

Specie Critical Pressure (kPa) Critical Temperature (K)

Air 37,700 133

Carbon Dioxide, CO

73,900 304

Carbon Monoxide, CO 35,000 133

Ethanol, C

OH 63,800 516

Hydrogen, H

13,000 33.2

Methanol, CH

OH 79,600 513

Nitrogen, N

33,900 126

Oxygen, O

50,500 154

Water, H

O 220,900 647.3

Source: Adapted from M. J. Moran and H. N. Shapiro, Fundamentals of Engineering Thermodynamics,3rd

Edition, Wiley, New York, 1995.

Table A . 2 Heats of Formation, Gibbs Heat of Formation, and Absolute Entropy of Selected Species

at STP Conditions (298 K and 1 atm)

Specie

(kJ/kmol)

(kJ/kmol K)

Carbon Dioxide, CO

−393,520 −394,380 213.69

Carbon Monoxide, CO −110,530 −137,150 197.54

Ethanol, C

−235,310 −168,570 282.59

Ethanol, C

−277,690 174,890 160.70

Hydrogen, H

0 0 130.57

Methane, CH4

−74,850 −50,790 186.16

Methanol, CH

−200,890 −162,140 239.70

Methanol, CH

−238,810 −166,290 126.80

Nitrogen, N

0 0 191.50

Oxygen, O

0 0 205.03

Water, H

−241,820 −228,590 188.72

Water, H

−285,830 −237,180 69.95

Source: Adapted from M. J. Moran and H. N. Shapiro, Fundamentals of Engineering Thermodynamics,3rd

Edition, Wiley, New York, 1995.

app JWPR067-Mench December 13, 2007 17:33 Char Count=

Appendix 487

Table A . 3 Ideal Gas Properties of Air

Th p

200 199.97 0.3363 142.56 1707. 1.29559

210 209.97 0.3987 149.69 1512. 1.34444

220 219.97 0.4690 156.82 1346. 1.39105

230 230.02 0.5477 164.00 1205. 1.43557

240 240.02 0.6355 171.13 1084. 1.47824

250 250.05 0.7329 178.28 979. 1.51917

260 260.09 0.8405 185.45 887.8 1.55848

270 270.11 0.9590 192.60 808.0 1.59634

280 280.13 1.0889 199.75 738.0 1.63279

285 285.14 1.1584 203.33 706.1 1.65055

290 290.16 1.2311 206.91 676.1 1.66802

295 295.17 1.3068 210.49 647.9 1.68515

300 300.19 1.3860 214.07 621.2 1.70203

305 305.22 1.4686 217.67 596.0 1.71865

310 310.24 1.5546 221.25 572.3 1.73498

315 315.27 1.6442 224.85 549.8 1.75106

320 320.29 1.7375 228.42 528.6 1.76690

325 325.31 1.8345 232.02 508.4 1.78249

330 330.34 1.9352 235.61 489.4 1.79783

340 340.42 2.149 242.82 454.1 1.82790

350 350.49 2.379 250.02 422.2 1.85708

360 360.58 2.626 257.24 393.4 1.88543

370 370.67 2.892 264.46 367.2 1.91313

380 380.77 3.176 271.69 343.4 1.94001

390 390.88 3.481 278.93 321.5 1.96633

400 400.98 3.806 286.16 301.6 1.99194

410 411.12 4.153 293.43 283.3 2.01699

420 421.26 4.522 300.69 266.6 2.04142

430 431.43 4.915 307.99 251.1 2.06533

440 441.61 5.332 315.30 236.8 2.08870

450 451.80 5.775 322.62 223.6 2.11161

460 462.02 6.245 329.97 211.4 2.13407

470 472.24 6.742 337.32 200.1 2.15604

480 482.49 7.268 344.70 189.5 2.17760

490 492.74 7.824 352.08 179.7 2.19876

500 503.02 8.411 359.49 170.6 2.21952

510 513.32 9.031 366.92 162.1 2.23993

520 523.63 9.684 374.36 154.1 2.25997

530 533.98 10.37 381.84 146.7 2.27967

540 544.35 11.10 389.34 139.7 2.29906

(Continued)

app JWPR067-Mench December 13, 2007 17:33 Char Count=

488 Appendix

Table A . 3 (Continued)

Thp

550 554.74 11.86 396.86 133.1 2.31809

560 565.17 12.66 404.42 127.0 2.33685

570 575.59 13.50 411.97 121.2 2.35531

580 586.04 14.38 419.55 115.7 2.37348

590 596.52 15.31 427.15 110.6 2.39140

600 607.02 16.28 434.78 105.8 2.40902

610 617.53 17.30 442.42 101.2 2.42644

620 628.07 18.36 450.09 96.92 2.44356

630 638.63 19.84 457.78 92.84 2.46048

640 649.22 20.64 465.50 88.99 2.47716

650 659.84 21.86 473.25 85.34 2.49364

660 670.47 23.13 481.01 81.89 2.50985

670 681.14 24.46 488.81 78.61 2.52589

680 691.82 25.85 496.62 75.50 2.54175

690 702.52 27.29 504.45 72.56 2.55731

700 713.27 28.80 512.33 69.76 2.57277

710 724.04 30.38 520.23 67.07 2.58810

720 734.82 32.02 528.14 64.53 2.60319

730 745.62 33.72 536.07 62.13 2.61803

740 756.44 35.50 544.02 59.82 2.63280

750 767.29 37.35 551.99 57.63 2.64737

760 778.18 39.27 560.01 55.54 2.66176

770 789.11 41.31 568.07 53.39 2.67595

780 800.03 43.35 576.12 51.64 2.69013

790 810.99 45.55 584.21 49.86 2.70400

800 821.95 47.75 592.30 48.08 2.71787

820 843.98 52.59 608.59 44.84 2.74504

840 866.08 57.60 624.95 41.85 2.77170

860 888.27 63.09 641.40 39.12 2.79783

880 910.56 68.98 657.95 36.61 2.82344

900 932.93 75.29 674.58 34.31 2.84856

920 955.38 82.05 691.28 32.18 2.87324

940 977.92 89.28 708.08 30.22 2.89748

960 1000.55 97.00 725.02 28.40 2.92128

980 1023.25 105.2 741.98 26.73 2.94468

1000 1046.04 114.0 758.94 25.17 2.96770

T (K), h and u (kJ/kg), s

(kJ/kg·K).

Source: Adapted from K. Wark, Thermodynamics, 4th ed., McGraw-Hill, New York, 1983, as based on J. H.

Keenan and J. Kaye, Gas Tables, Wiley, New York, 1945.

app JWPR067-Mench December 13, 2007 17:33 Char Count=

Appendix 489

Table A . 4 Ideal Gas Properties of Carbon Dioxide (CO

)

000 0

220 6,601 4,772 202.966

230 6,938 5,026 204.464

240 7,280 5,285 205.920

250 7,627 5,548 207.337

260 7,979 5,817 208.717

270 8,335 6,091 210.062

280 8,697 6,369 211.376

290 9,063 6,651 212.660

298 9,364 6,885 213.685

300 9,431 6,939 213.915

310 9,807 7,230 215.146

320 10,186 7,526 216.351

330 10,570 7,826 217.534

340 10,959 8,131 218.694

350 11,351 8,439 219.831

360 11,748 8,752 220.948

370 12,148 9,068 222.044

380 12,552 9,392 223.122

390 12,960 9,718 224.182

400 13,372 10,046 225.225

410 13,787 10,378 226.250

420 14,206 10,714 227.258

430 14,628 11,053 228.252

440 15,054 11,393 229.230

450 15,483 11,742 230.194

460 15,916 12,091 231.144

470 16,351 12,444 232.080

480 16,791 12,800 233.004

490 17,232 13,158 233.916

500 17,678 13,521 234.814

510 18,126 13,885 235.700

520 18,576 14,253 236.575

530 19,029 14,622 237.439

540 19,485 14,996 238.292

550 19,945 15,372 239.135

560 20,407 15,751 239.962

570 20,870 16,131 240.789

580 21,337 16,515 241.602

590 21,807 16,902 242.405

(Continued)