Journal of Applied Electrochemistry

, Volume 10, Issue 1, pp 109–125 | Cite as

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

  • R. Barnard
  • C. F. Randell
  • F. L. Tye


Reversible potentials (ER) 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 thatER is independent of the degree of oxidation of the nickel cation between states of charge of 25% and 70%. SimilarlyER 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.


Oxidation Physical Chemistry Nickel Hydroxide Crystal Lattice 
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Copyright information

© Chapman and Hall Ltd 1980

Authors and Affiliations

  • R. Barnard
    • 1
  • C. F. Randell
    • 1
  • F. L. Tye
    • 1
  1. 1.Berec Group LimitedGroup Technical CentreLondonUK

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