Journal of Applied Electrochemistry

, Volume 15, Issue 2, pp 159–166 | Cite as

Positive polyacetylene electrodes in aqueous electrolytes

  • K. H. Dietz
  • F. Beck
Papers
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Abstract

Polyacetylene films, contacted with platinum mesh, have been polarized anodically in aqueous H2SO4, HClO4, HBF4 and H2F2 of medium concentrations (30–70 wt%). Two oxidation peaks are observed, the equivalents of which are
$${\text{(1) 0}}{\text{.045 F mol}}^{ - {\text{1}}} {\text{ CH (2) 0}}{\text{.23 F mol}}^{ - {\text{1}}} {\text{ CH}}$$
(1)
The potential of the Process 1 decreases linearly with increasing acid concentration by 20–40 mV mol−1 dm−3, while the potential of Peak 2 exhibits normal Nernst behaviour (about + 60 mV decade−1. Process 1 is partially reversible, while Process 2 is totally irreversible. From these findings for Process 1 we conclude the reversible insertion of anions into the polyacetylene host lattice, which is primarily oxidized to the polyradical cation, with the co-insertion of acid molecules HA to yield the insertion compound [(CH)+·yA−·vyHA] x y⩽4.5% andv=1.5 for H2SO4 and HClO4. In the course of Process 2, the polymer is irreversibly oxidized according to
$$( - ^ \cdot {\text{CH}} \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot ^ \oplus {\text{ CH}} - )_{x/2} + 2{\text{H}}_{\text{2}} {\text{O}} \to ( - \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } - )_{x/2} + 6{\text{H}}^{\text{ + }} + 5e^ - $$

As this process occurs to some extent even in the potential region of Process 1, a continuous degradation of the host lattice occurs upon cycling.

Keywords

H2SO4 HClO4 Potential Region Oxidation Peak Medium Concentration 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References

  1. [1]
    C. K. Chiang, M. A. Druy, S. C. Gau, A. J. Heeger, E. J. Louis, A. G. McDiarmid, Y. W. Park and H. Shirakawa,J. Amer. Chem. Soc. 100 (1978) 1013.Google Scholar
  2. [2]
    A. G. McDiarmid and A. J. Heeger,Synth. Metals 1 (1979/80) 101.Google Scholar
  3. [3]
    R. H. Baughman, S. L. Hsu, G. P. Pez and A. J. Signorelli,J. Chem. Phys. 68 (1978) 5405.Google Scholar
  4. [4]
    M. Monkenbusch, B. S. Morra and G. Wegner,Makromol. Chem. Rapid Commun. 3 (1982) 69.Google Scholar
  5. [5]
    S. R. Henning,Prog. Inorg. Chem. 1 (1959) 125.Google Scholar
  6. [6]
    L. B. Ebert,Ann. Rev. Mater. Sci. 6 (1976) 181. (Especially p. 196).Google Scholar
  7. [7]
    P. J. Nigrey, A. G. McDiarmid and A. J. Heeger,J. Chem. Soc. Chem. Commun. (1979) 594.Google Scholar
  8. [8]
    Idem, ibid. (1981) 317.Google Scholar
  9. [9]
    P. J. Nigrey, D. McInnes, D. P. Nairns, A. G. McDiarmid and A. J. Heeger,J. Electrochem. Soc. 128 (1981) 1651.Google Scholar
  10. [10]
    A. G. McDiarmid, A. J. Heeger and P. J. Nigrey, European Patent 36 118 (1981).Google Scholar
  11. [11]
    H. Shirakawa and S. Ikeda,Polym. J. 2 (1971) 231.Google Scholar
  12. [12]
    Idem, J. Polym. Chem. Ed. 12 (1974) 11.Google Scholar
  13. [13]
    J. Hocker, W. Wieder and R. Dhein, European Patent 45 908 (1981).Google Scholar
  14. [14]
    R. T. Gray, European Patent 50 441 (1981).Google Scholar
  15. [15]
    R. B. Kaner, A. G. McDiarmid and R. J. Mammone, ACS Symposium Series ‘Polymers in Electronics’, Washington 1984.Google Scholar
  16. [16]
    A. Guiseppi-Elie and G. E. Wnek,J. Chem. Soc. Chem. Commun. (1983) 63.Google Scholar
  17. [17]
    F. Beck, H. Junge and H. Krohn,Electrochim. Acta 26 (1981) 799.Google Scholar
  18. [18]
    Idem, Ber. Bunsenges. Phys. Chem. 86 (1982) 704.Google Scholar
  19. [19]
    F. Beck and H. Krohn, Proceedings of the Symposium ‘Electrochemistry of Carbon’, Cleveland 17–19 August 1983 (Edited by E. Yeageret al.) The Electrochemical Society, Princeton, 1984.Google Scholar
  20. [20]
    F. Beck and A. Pruß,Electrochim. Acta 28 (1983) 1847.Google Scholar
  21. [21]
    Idem, J. Electroanal. Chem. 172 (1984) 281.Google Scholar
  22. [22]
    F. Beck, W. Kaiser and H. Krohn,Angew. Chem. Suppl. (1982) 57.Google Scholar
  23. [23]
    F. Beck and W. Kaiser, Unpublished results.Google Scholar
  24. [24]
    D. Nägele and R. Bittihn, ISE Meeting, September 1983, DECHEMA Monographien (1984).Google Scholar
  25. [25]
    E. Rhodes, ‘Power Sources’ (edited by D. H. Collins) Oxford (1967) p. 1.Google Scholar
  26. [26]
    H. Krohn, F. Beck and R. Herrmann,Chem. -Ing. Techn. 54 (1982) 530.Google Scholar
  27. [27]
    F. Will, Electrochemical Society Meeting, San Francisco, May 1983, Extended Abstract No. 554.Google Scholar
  28. [28]
    H. W. Salzberg and M. Leung,J. Org. Chem. 30 (1965) 2873.Google Scholar
  29. [29]
    L. Eberson,J. Amer. Chem. Soc. 89 (1967) 4669.Google Scholar
  30. [30]
    H. P. Boehm, M. Eckel and W. Scholz,Zh. Anorg. Allg. Chem. 353 (1967) 236.Google Scholar
  31. [31]
    K. Kaneto, M. Maxfield, D. P. Nairns, A. G. McDiarmid and A. J. Heeger,J. Chem. Soc. Farad. Trans. 1 78 (1982) 3417.Google Scholar

Copyright information

© Chapman and Hall Ltd. 1985

Authors and Affiliations

  • K. H. Dietz
    • 1
  • F. Beck
    • 1
  1. 1.University -GH-Duisburg, FB 6 ElektrochemieDuisburg 1West Germany

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