Skip to main content
SpringerLink
Log in

Studies concerning charged nickel hydroxide electrodes I. Measurement of reversible potentials

  • Papers
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

Reversible potentials (E R) have been measured for nickel hydroxide/oxyhydroxide couples over a range of KOH concentrations from 0·01–10 M. It is shown that the couples derived from the parentα- andβ-Ni(OH)2 systems can be distinguished by the relative change in KOH level on oxidation and reduction. In the case of couples derived from theα-class of materials a dependence of 0·470 moles of KOH per 2e change is found compared with 0·102 moles of KOH per 2e change for theβ-class of materials. Couples derived from theα- andβ-Ni(OH)2 systems can be encountered in a series of ‘activated’ and ‘de-activated’ forms having a range of formal potentialsE ′0 . ‘Activated’. and ‘de-activated’β-Ni(OH)2/β-NiOOH couples are found to lie in the range 0·443–0·470 V whilstα-Ni(OH)2/γ-NiOOH couples lie in the range 0·392–0·440 V w.r.t. Hg/HgO/KOH. It is demonstrated for ‘de-activated’,β-Ni(OH)2/β-NiOOH couples thatE R is independent of the degree of oxidation of the nickel cation between states of charge of 25% and 70%. SimilarlyE R is constant for states of charge between 12% and 60% for ‘activated’α-Ni(OH)2/γ-NiOOH couples. The constant potential regions are considered to be derived from heterogeneous equilibria between pairs of co-existing phases both containing nickel in upper and lower states of oxidation. Differences inE ′0 between the ‘activated’ and ‘de-activated’ couples are considered to be related to the degree of order/disorder in the crystal lattice.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. P. C. Milner and U. B. Thomas, in ‘Advances in Electrochemistry and Electrochemical Engineering’ Vol. 5, Interscience, New York (1967) p. 42.

    Google Scholar 

  2. J. P. Hoare, ‘The Electrochemistry of Oxygen’ Interscience, New York (1968).

    Google Scholar 

  3. S. U. Falk and A. J. Salkind, ‘Alkaline Storage Batteries’, Wiley and Sons, London, New York (1969) p. 48.

    Google Scholar 

  4. G. W. D. Briggs,Chem. Soc. Specialist Periodical Reports, Electrochemistry 4 (1974) 33.

    Google Scholar 

  5. D. J. Ives and G. J. Janz, ‘Reference Electrodes’, Academic Press, New York, London (1961) p. 331.

    Google Scholar 

  6. J. Zedner,Z. Elektrochem. 11 (1905) 809.

    Google Scholar 

  7. Idem, ibid 12 (1906) 463.

    Google Scholar 

  8. Idem, ibid 13 (1907) 752.

    Google Scholar 

  9. F. Foerster,Z. Elektrochem. 13 (1907) 414.

    Google Scholar 

  10. Idem, ibid 14 (1908) 285.

    Google Scholar 

  11. J. Besson,C.R. Acad. Sci. Paris 23 (1946) 28.

    Google Scholar 

  12. F. Kornfeil,Proc. 12th US Army Battery Research and Development Conference (1958) p. 22.

  13. B. E. Conway and P. L. Bourgault,Canad. J. Chem. 37 (1959) 292.

    Google Scholar 

  14. Idem, ibid 38 (1960) 1557.

    Google Scholar 

  15. Idem, ibidB. E. Conway and P. L. Bourgault,Canad. J. Chem. 40 (1962) 1690.

    Google Scholar 

  16. B. E. Conway and P. L. Bourgault,Trans. Faraday. Soc. 58 (1962) 593.

    Google Scholar 

  17. B. E. Conway and E. Gileadi,Canad. J. Chem. 40 (1962) 1933.

    Google Scholar 

  18. H. Bode, K. Dehmelt and J. Witte,Electrochim. Acta 11 (1966) 1079.

    Google Scholar 

  19. H. Bode, K. Dehemelt and J. Witte,Z. Anorg. Allg. Chem. 1 (1969) 366.

    Google Scholar 

  20. E. A. Kaminskaya, N. Yu. Uflyand and S. A. Rozenteveig,Sbornik. Rab. Khim. Istochnikam Toka 4 (1969) 13.

    Google Scholar 

  21. N. Yu. Uflyand, A. M. Novakovskii and S. A. Osentsveig,Electrokhimiya 3 (1967) 537.

    Google Scholar 

  22. R. Barnard, G. T. Crickmore, J. A. Lee and F. L. Tye,J. Appl. Electrochem.

  23. D. M. MacArthur,J. Electrochem. Soc. 117 (1970) 422.

    Google Scholar 

  24. P. Kelson, A. D. Sperrin and F. L. Tye, ‘Power Sources 4’, edited by D. H. Collins, Oriel Press (1973) p. 201.

  25. E. Hausler, ‘Power Sources’ edited by D. H. Collins, Pergamon Press (1966) p. 287.

  26. R. S. McEwen,J. Phys. Chem. 75 (1971) 1782.

    Google Scholar 

  27. G. W. D. Briggs and W. F. K. Wynne-Jones,Electrochim. Acta 7 (1962) 241.

    Google Scholar 

  28. A. B. Scott,J. Electrochem. Soc. 107 (1960) 941.

    Google Scholar 

  29. K. V. Kordesch, ‘Batteries’ Vol. 1 ‘Manganese Dioxide’ edited by K. V. Kordesch, Marcel Dekker, N.Y. (1974) p. 82, 84.

    Google Scholar 

  30. W. Fischer,Electrochim. Acta 21 (1976) 1001.

    Google Scholar 

  31. Idem, Paper presented atEuchem. Conference Le Hohwald (1977).

  32. L. N. Sagoyan, Yu. M. Gulamov, P. Z. Barsukov and V. E. Dmitrenko,28th ISE Meeting, Bulgaria (1977) Extended Abstract no. 82.

  33. D. Tuomi,J. Electrochem. Soc. 112 (1965) 1.

    Google Scholar 

  34. A. A. Yakovleva and Yu. N. Chernykh,Electrokhimiyia 6 (1970) 1671.

    Google Scholar 

  35. P. D. Lukovstev,Soviet Electrochem. 3 (1961) 156.

    Google Scholar 

  36. G. W. D. Briggs and M. Fleischmann,Trans. Faraday Soc. 67 (1971) 2397.

    Google Scholar 

  37. O. Glemser and J. Einerhand,Z. Anorg. Chem. 261 (1950) 26.

    Google Scholar 

  38. R. Barnard, C. F. Randell and F. L. Tye,J. Appl. Electrochem., to be published.

  39. G. N. Lewis and M. Randall, ‘Thermodynamics’, McGraw-Hill Co, New York, London (1932) p. 327.

    Google Scholar 

  40. G. C. Akerlof and P. Bender,J. Amer. Chem. Soc. 70 (1948) 2366.

    Google Scholar 

  41. G. C. Akerlof and C. Kegeles,ibid 62 (1940) 620.

    Google Scholar 

  42. H. Bartl, H. Bode, G. Sterr and J. Witte,Electrochim. Acta 16 (1971) 615.

    Google Scholar 

  43. V. A. Volynskii and Yu. N. Chernykh,Electrokhimiya 13 (1977) 1874.

    Google Scholar 

  44. J. Labat,Ann Chim. 9 (1964) 399.

    Google Scholar 

  45. S. A. Aleshkevich, E. J. Golovchenko, V. P. Morozov and L. N. Sagoyan,Soviet Electrochem. 4 (1968) 530, 1117.

    Google Scholar 

  46. O. Rademacher, K. Wiesener and E. Prikryl,Z. Phys. Chem. 258 (1977) 113.

    Google Scholar 

  47. IUPAC ‘Selected Constants’, edited by G. Charlot, Butterworths, London (1971) p. 34.

    Google Scholar 

  48. R. Barnard, G. T. Crickmore, J. A. Lee and F. L. Tye, ‘Power Sources 6’, edited by D. H. Collins, Academic Press (1977) p. 161.

Download references

Author information

Authors and Affiliations

  1. Berec Group Limited, Group Technical Centre, St Ann's Road, N15, London, UK

    R. Barnard, C. F. Randell & F. L. Tye

Authors
  1. R. Barnard
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. C. F. Randell
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. L. Tye
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Barnard, R., Randell, C.F. & Tye, F.L. Studies concerning charged nickel hydroxide electrodes I. Measurement of reversible potentials. J Appl Electrochem 10, 109–125 (1980). https://doi.org/10.1007/BF00937345

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00937345

Keywords

Search

Navigation