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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solid state electrochemistry 2 (1998), S. 401-404 
    ISSN: 1433-0768
    Keywords: Key words Insertion electrode ; Cyclic voltammetry ; Electrolyte concentration ; Mass transport ; Solid-state electrochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A solid-state redox reaction involving an insertion of ions is analyzed with respect to the influence of the concentration of inserting ions in the solution phase. The voltammetric response is independent of the mass transfer in the solution provided that z = (D ss/D aq)1/2 ρ/[C+]* is smaller than 0.1 (D ss: diffusion coefficient of the cation C+ in the crystal; D aq: diffusion coefficient of the cation C+ in the solution; ρ: density of the solid compound; [C+]*: concentration of cations in the bulk of the solution). In real cases this condition will be satisfied at solution concentrations above 1 mol/l.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solid state electrochemistry 4 (2000), S. 394-401 
    ISSN: 1433-0768
    Keywords: Key words Miscibility gap ; Mixed phases ; Cyclic voltammetry ; Solid state electrochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyclic voltammograms of electroactive solid compounds with partial immiscibility between the oxidized and reduced phases can exhibit a splitting of the peaks. If the free energy of transformation between the oxidized and reduced phases is small, the formal potentials of the redox pair will be almost the same in both solid phases. This results in an inert potential range in which no appreciable electrochemical activity is possible. The kinetic implications of this situation have been analysed in relation to the width of the miscibility gap. The diffusion of ions in the particle, which is hindered by the immiscibility, can proceed when a transition zone between the two phases exists in which the crystal structure is changed. If there is no such transition zone the voltammogram will display several spikes, which are caused by the collapse of concentration barriers at the sharp interfaces between the two phases in the mixed crystals.
    Type of Medium: Electronic Resource
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