Journal of Applied Electrochemistry

, Volume 12, Issue 1, pp 101–108 | Cite as

On the manganese dioxide electrode. V. The evidence indicating the presence of two solid solutions in the range MnO2-MnO1·5 with γ-MnO2 as one end member

  • W. C. Maskell
  • J. A. E. Shaw
  • F. L. Tye


An examination of the literature has revealed that several of the properties of oxyhydroxides derived fromγ-MnO2 show a sharp change around the midpoint at MnO1.75. These include the lattice parameters, the activation energy for semiconduction, the magnetic susceptibility, the thermal behaviour and the electrical potential. Intermediate compounds have been observed by X-ray diffraction in the closely related systems ramsdellite/groutite and VO2/VOOH. It is suggested that for theγ-MnO2/δ-MnOOH system two solid solutions exist, one between MnO2 and MnO1.75 (e.g. Mn2O4H) and another between Mn2O4H and MnOOH. Ways in which the two solid solutions may arise involving different proton-electron filling mechanisms above and below the midpoint are discussed.


Physical Chemistry Dioxide Activation Energy Manganese Solid Solution 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    E. Divers,Chem. News 46 (1882) 259.Google Scholar
  2. [2]
    A. Keller,Z. Elektrochem. 37 (1931) 342.Google Scholar
  3. [3]
    W. C. Vosburgh,J. Electrochem. Soc. 106 (1959) 839.Google Scholar
  4. [4]
    J. Caudle, K. G. Summer and F. L. Tye,J. Chem. Soc. Faraday Trans. I 69 (1973) 876.Google Scholar
  5. [5]
    Idem, ibid. 69 (1973) 885.Google Scholar
  6. [6]
    F. Kornfeil,J. Electrochem. Soc. 109 (1962) 349.Google Scholar
  7. [7]
    A. Kozawa, ‘Batteries, Vol. 1, Manganese Dioxide’, (edited by K. V. Kordesch) Marcel Dekker, New York (1974) p. 385.Google Scholar
  8. [8]
    A. B. Scott,J. Electrochem. Soc. 107 (1960) 941.Google Scholar
  9. [9]
    P. M. de Wolff,Acta Crystall. 12 (1959) 341.Google Scholar
  10. [10]
    A. M. Bystrom,Acta Chem Scand. 3 (1949) 163.Google Scholar
  11. [11]
    J. Brenet,CITCE Conference, Madrid (1956).Google Scholar
  12. [12]
    W. Feitknecht, H. R. Oswald and U. Feitknecht-Steinmann,Helv. Chim. Acta 43 (1960) 1947.Google Scholar
  13. [13]
    J. F. Laurent and B. Morignat, ‘Batteries’, (edited by D. H. Collins), Pergamon, Oxford (1963) p. 309.Google Scholar
  14. [14]
    J. P. Gabano, B. Morignat, E. Fialdes, B. Emery and J. F. Laurent,Z. Phys. Chem. 46 (1965) 359.Google Scholar
  15. [15]
    W. C. Maskell, J. E. A. Shaw and F. L. Tye,Electrochim. Acta 26 (1981) 1403.Google Scholar
  16. [16]
    R. Giovanoli, K. Bernhard and W. Feitknecht,Helv. Chim. Acta 51 (1968) 355.Google Scholar
  17. [17]
    J. P. Gabano, B. Morignat and J. F. Laurent,Electrochem. Technol. 5 (1967) 531.Google Scholar
  18. [18]
    J. A. Lee, C. E. Newnham, F. L. Tye and F. S. Stone,J. Chem. Soc. Faraday Trans. I 74 (1978) 237.Google Scholar
  19. [19]
    Ph. Brouillet, A. Grund, F. Jolas and R. Mellet, ‘Batteries 2’, (edited by D. H. Collins), Pergamon, Oxford (1965) p. 189.Google Scholar
  20. [20]
    H. Bode and A. Schmier, ‘Batteries’, (edited by D. H. Collins), Pergamon, Oxford (1963) p. 329.Google Scholar
  21. [21]
    G. S. Bell and R. Huber,J. Electrochem. Soc. 111 (1964) 1.Google Scholar
  22. [22]
    K. Neumann and E. von Roda,Ber. Bunsenges. Phys. Chem. 69 (1965) 347.Google Scholar
  23. [23]
    K. J. Vetter and N. Jaeger,Electrochim. Acta 11 (1966) 401.Google Scholar
  24. [24]
    A. Kozawa and R. A. Powers,Electrochem. Technol. 5 (1967) 535.Google Scholar
  25. [25]
    K. J. Vetter,Z. Elektrochem. 66 (1962) 577.Google Scholar
  26. [26]
    W. C. Maskell, J. A. E. Shaw and F. L. Tye, unpublished work (1980).Google Scholar
  27. [27]
    C. Klingsberg and R. Roy,Amer. Mineral. 44 (1959) 819.Google Scholar
  28. [28]
    H. T. Evans and M. E. Mrose,ibid. 40 (1955) 861.Google Scholar
  29. [29]
    J. Muller and J. C. Joubert,J. Solid State Chem. 11 (1974) 79.Google Scholar
  30. [30]
    S. Atlung, ‘Manganese Dioxide Symposium’, Vol. 1, (compiled by A. Kozawa and R. J. Brodd), Electrochem. Soc., Cleveland, Ohio (1975) p. 47.Google Scholar
  31. [31]
    L. S. Dent-Glasser and L. Ingram,Acta Cryst. B24 (1968) 1233.Google Scholar
  32. [32]
    R. G. Burns and V. M. Burns, ‘Manganese Dioxide Symposium’, Vol. 1, (compiled by A. Kozawa and R. J. Brodd), Electrochem. Soc., Cleveland, Ohio (1975) p. 306.Google Scholar
  33. [33]
    R. Giovanoli and U. Leuenberger,Helv. Chim. Acta 52 (1969) 2333.Google Scholar
  34. [34]
    F. L. Tye,Electrochim. Acta 21 (1976) 415.Google Scholar

Copyright information

© Chapman and Hall Ltd. 1982

Authors and Affiliations

  • W. C. Maskell
    • 1
  • J. A. E. Shaw
    • 1
  • F. L. Tye
    • 1
  1. 1.Group Technical CentreBerec Group LtdLondonUK

Personalised recommendations