4.6 Article

Electrochemical behaviour of the β(II)-Ni(OH)2/β(III)-NiOOH redox couple upon potentiodynamic cycling conditions

Journal

ELECTROCHIMICA ACTA
Volume 51, Issue 25, Pages 5430-5437

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2006.02.012

Keywords

nickel (oxy)hydroxide; cyclic voltammetry; secondary reduction step or discharge plateau; structure; Raman spectroscopy; ellipsometry

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The electrochemical behaviour of pure and Co-doped Ni(OH)(2) powders is investigated under potentiodynamic cycling conditions. Evolution ofsome beta-Ni(OH)(2) physical properties as a function of the oxidation state is followed by ex situ Surface Enhanced mu-Raman Spectroscopy and in situ Ellipsometry. Effects related to the first and second reduction steps, as well as to the sweeping rate, are qualitatively studied. When compared to the results that have been recently obtained under galvanostatic conditions [S. Deabate, F. Henn, Electrochim. Acta 50 (2005) 2823], the present work confirms that the second reduction process is strongly associated to the occurrence of a reduced phase, i.e. NiO2H2-epsilon, with 0 < epsilon < similar to 0.3, at the surface of the active mass grains. This reduced phase exhibits spectroscopic features very similar to the initial hydroxide which is known to be highly insulating in regards to both electrons and protons transfer. (c) 2006 Elsevier Ltd. All rights reserved.

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