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Studies concerning charged nickel hydroxide electrodes. II. Thermodynamic considerations of the reversible potentials

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Abstract

In this paper the thermodynamics of mixing are applied to account for the independence of the discharge potential of the nickel hydroxide electrode as a function of nickel oxidation state. The constant potential region is considered to arise from the formation of a pair of co-existing solid solutions having a composition predetermined by the magnitude of the interactions between the oxidized and reduced species. From considerations of the excess-energy terms, it can be shown for a symmetrical potential/ composition profile, that the constant potential region is identical with the standard potentialE 0. The influence of asymmetry on the changes inE 0 are discussed. Consideration has also been made of the influence of dissociation of oxidized and/or reduced species on the potential determining equations. The removal of n-type defects from the nickel(II)-rich phase on discharge is considered to be responsible for the observed secondary discharge plateau at potentials ∼ 300 mV more cathodic than normal. This non-equilibrium behaviour can be explained in terms of a mixed pn-semiconducting material.

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Abbreviations

E :

electrode potential at constant pH(V)

E 0 :

standard electrode potential (V)

R :

the gas constant (J K−1 mole−1)

F :

the Faraday constant (C g-equiv−1)

T :

the absolute temperature (K)

aH+ :

proton activity in the electrolyte

a z :

activity of oxidized species z

a y :

activity of reduced species y

μH+:

chemical potential of the proton

μ e :

chemical potential of the electron

μ oz :

standard chemical potential of species z

μ z :

chemical potential of species z

μ oy :

standard chemical potential of species y

μ y :

chemical potential of species y

μ H,e :

chemical potential of the proton/electron pair

x y orx :

mole fraction of reduced species y

x z :

mole fraction of oxidized species z

G M :

total free energy of mixing (J mole−1)

G R :

free energy of reaction (J mole−1)

G I :

free energy of mixing under ideality (J mole−1)

G E :

excess free energy (J mole−1)

A,A i andB i :

interaction energy parameters (J mole−1)

x u :

mole fraction of y in co-existing phase u

x v :

mole fraction of y in co-existing phase v

γ y :

activity coefficient of undissociated reduced species y

γ z :

activity coefficient of undissociated oxidized species z

γ ±y :

mean ionic activity coefficient of y

γ ±z :

mean ionic activity coefficient of z

γ υy :

activity coefficient of y in phase u

γ uz :

activity coefficient of z in phase u

γ vy :

activity coefficient of y in phase v

γ vz :

activity coefficient of z in phase v

I :

current (A)

S:

cross-sectional area (cm2)

L:

conductor length (cm)

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Authors and Affiliations

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

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

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  1. R. Barnard
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  2. C. F. Randell
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  3. F. L. Tye
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Barnard, R., Randell, C.F. & Tye, F.L. Studies concerning charged nickel hydroxide electrodes. II. Thermodynamic considerations of the reversible potentials. J Appl Electrochem 10, 127–141 (1980). https://doi.org/10.1007/BF00937346

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