Journal of Applied Electrochemistry

, Volume 37, Issue 1, pp 103–110 | Cite as

Investigation of the response of separate electrodes in a polymer electrolyte membrane fuel cell without reference electrode

  • Mathieu Boillot
  • Caroline Bonnet
  • Sophie Didierjean
  • François Lapicque
Article
First Online:
Received:
Revised:
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Abstract

The paper presents electrochemical measurements carried out in a PEMFC with a view to determining the separate kinetics of the electrode reactions. For this purpose, the separate response of one electrode (anode or cathode) was magnified by dilution of the reacting gas, respectively hydrogen and oxygen, and comparison of the experimental data in the form of steady voltage-current variations and impedance spectra. Experiments were carried out at 60 °C and ambient pressure. Water management was thoroughly controlled so that the gases leaving the cell had the same relative humidity in all experiments of one series. Hydrogen oxidation, although rapid, corresponds to overpotentials up to 50 mV at high dilution rates and current densities. Assuming a Tafel–Volmer mechanism, the exchange current density of the anode reaction at the Pt surface is of the order of 1 mA cm−2. The two techniques employed led to Tafel slopes of oxygen reduction ranging from 120 to 150 mV/decade, with an exchange current density near 1 μA cm−2, in good agreement with published data.

Keywords

electrochemical investigation hydrogen oxidation impedance spectroscopy oxygen reduction PEM Fuel cells 

Abbreviations

bT

Tafel coefficient, V/decade

C

concentration, mol m−3

D

diffusion coefficient, m2 s−1

e

electron

F

Faraday’s constant, 96487 C mol−1

I

current, A

i

current density, A m−2 or A cm−2

iL

limiting current density, A m−2 or A cm−2

i0

exchange current density, A m−2 or A cm−2

J

specific flux mol m−2 s−1

m

partitioning coefficient

n

number of electrons involved

P

pressure, Atm

Q

pseudocapacitance, S cm−2 sα

R

gas constant, 8.314 J K−1 mol−1

r

specific resistance, Ω cm2

T

temperature, K

Urev

reversible voltage, V

V

cell voltage, V

Z

impedance, Ω

Greek letters

α

exponent of constant phase element

α

charge transfer coefficient

γ

ration of effective area over geometrical area

δ

layer thickness, m

ɛ

porosity

η

overpotential, V

∞

bulk conditions

Subscripts

a

anode

c

cathode

CPE

constant phase element

ct

charge transfer

diff

diffusion

eff

effective

L

limiting

N

Nafion

ohm

ohmic

Ox

oxidant

Red

reductant

0

electrode surface

1

gas diffusion electrode

2

electrode structure

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Notes

Acknowledgements

The authors are indebted to Region Lorraine and CNRS for funding facilities – through PACEM “PRI” – and the Ph.D. grant allocated to M.B.

References

  1. 1.
    Li G., Pickup P.G. (2004). Electrochim. Acta 49:4119CrossRefGoogle Scholar
  2. 2.
    Liu Z., Wainright J.S., Huang W., Savinell R.F. (2004). Electrochim. Acta 49:923CrossRefGoogle Scholar
  3. 3.
    Z. Siroma, R. Kakitsubo, N. Fujiwara, T. Ioroi, S.I. Yamazaki and K. Yasuda. (2006) J. Power Sources 156:284CrossRefGoogle Scholar
  4. 4.
    Kuhn H., Andreaus B., Wokaun A., Scherer G.G. (2005). Electrochim. Acta 51:1622CrossRefGoogle Scholar
  5. 5.
    Freire T.J.P., Gonzales E.R. (2001). J. Electroanal. Chem. 503:57CrossRefGoogle Scholar
  6. 6.
    Paganin V.A., Oliveira C.L.F., Ticianelli E.A., Springer T.E., Gonzales E.R. (1998). Electrochim. Acta 43:3761CrossRefGoogle Scholar
  7. 7.
    Boillot M., Bonnet C., Jatroudakis N., Carré P., Didierjean S., Lapicque F. (2005). Fuel Cells 6:31CrossRefGoogle Scholar
  8. 8.
    Sluyters-Rehbach M. (1994). Pure Appl. Chem. 66:1831Google Scholar
  9. 9.
    Boukamp B.A. (1986). Solid State Ionics 20:31CrossRefGoogle Scholar
  10. 10.
    Springer T.E., Zawodzinski T.A., Wilson M.S., Gottesfeld S. (1996). J. Electrochem. Soc. 143:587CrossRefGoogle Scholar
  11. 11.
    Gode P., Jaouen F., Lindbergh G., Lundblad A., Sundholm G. (2003). Electrochim. Acta 48:4175CrossRefGoogle Scholar
  12. 12.
    Bernardi D.M., Verbrugge M.W. (1991). AIChE J. 37:1151CrossRefGoogle Scholar
  13. 13.
    Ciureanu M., Roberge R. (2001). J. Phys. Chem. B 105:3531CrossRefGoogle Scholar
  14. 14.
    Vermeijlen J., Janssen L.J.J., Visser G.J. (1997). J. Appl. Electrochem. 27:497CrossRefGoogle Scholar
  15. 15.
    Conway B.E., Tilak B.V. (2002). Electrochim. Acta 47:3571CrossRefGoogle Scholar
  16. 16.
    Mello R.M.Q., Ticianelli E.A. (1997). Electrochim. Acta 42:1031CrossRefGoogle Scholar
  17. 17.
    Conway B.E., Bai L. (1986). J. Electroanal. Chem. 198:149CrossRefGoogle Scholar
  18. 18.
    Tilak B.V., Chen C.P. (1993). J. Appl. Electrochem. 23:631CrossRefGoogle Scholar
  19. 19.
    Parthasarathy A., Srinivasan S., Appleby A.J., Martin C.R. (1992). J. Electrochem. Soc. 139:2530CrossRefGoogle Scholar
  20. 20.
    Basura V.I., Beattie P.D., Holdcroft S. (1998). J. Electroanal. Chem. 458:1CrossRefGoogle Scholar
  21. 21.
    Sepa D.B., Vojnovic M.V. (1980). Electrochim. Acta 25:1491CrossRefGoogle Scholar
  22. 22.
    Damjanovic A., Sepa D.B., Vojnovic M.J. (1979). Electrochim. Acta 24:887CrossRefGoogle Scholar
  23. 23.
    Zhang L., Ma C., Mukerjee S. (2004). J. Electroanal. Chem. 568:273CrossRefGoogle Scholar
  24. 24.
    Antoine O., Bultel Y., Durand R. (2001). J. Electroanal. Chem. 499:85CrossRefGoogle Scholar
  25. 25.
    Boillot M., Validation expérimentale d’outils de modélisation d’une pile à combustible de type PEM, Ph.D dissertation, (INPL, Nancy 2005)Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  • Mathieu Boillot
    • 1
  • Caroline Bonnet
    • 1
  • Sophie Didierjean
    • 2
  • François Lapicque
    • 1
  1. 1.Laboratoire des Sciences du Génie ChimiqueCNRS-ENSIC-INPLNancyFrance
  2. 2.Laboratoire d’Energétique et de Mécanique Théorique et AppliquéeINPL-UHPVandœuvre les NancyFrance

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