Journal of the Electrochemical Society, Vol.147, No.4, 1306-1313, 2000
Electrochemical behavior of cobalt hydroxide used as additive in the nickel hydroxide electrode
As an attempt to understand better how cobalt hydroxide additives improve the nickel electrode performance, the Co(OH)(2)/CoOOH redox system has been investigated through electrochemical cycling starting from a commerical Co(OH)(2) sample. A study of the influence of texture and morphology as well as cycling parameters was performed. For charge rates greater than C/5, relative to the amount of Co(OH)(2), the electrochemical oxidation was found to be a solid-state process. This process led to a nonstoichiometric Cox4+Co1-x3+OOH1-x phase having a mosaic texture with enhanced electronic conductivity due to the presence of Co4+ ions. For lower charge rates (C/100), the reaction rate is slower, and Co2+ can dissolve in the electrolyte, leading to a less conductive phase having a stoichiometric composition (CoOOH) and a monolithic texture. When present, the Co4+ ions are reduced to Co3+, at 1.05 V while other reductions Co3+ --> Co2+ and Co2+ --> Co degrees take place at a lower potential, 0.67 and 0.0 V, respectively. These two reactions an both associated with a dissolution of Co(II) species, followed by a migration of cobalt toward the current collector, with the overall result being an electrode degradation