Studying the effects of bismuth on the electrochemical properties of lead dioxide layers by using the in situ EQCM techn
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ORIGINAL PAPER
Studying the effects of bismuth on the electrochemical properties of lead dioxide layers by using the in situ EQCM technique Balázs Broda 1 & György Inzelt 1 Received: 11 March 2020 / Revised: 19 March 2020 / Accepted: 19 March 2020 # The Author(s) 2020
Abstract The charge-discharge characteristics and the aging mechanism of PbO2 layers doped with bismuth in contact with sulfuric acid solutions were studied by using combined cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) techniques. For this purpose, thick lead dioxide layers (non-doped and doped with Bi) were electrodeposited on gold substrate from aqueous solutions of Pb(NO3)2 dissolved in nitric acid and they were investigated in sulfuric acid media. Based on the electrochemical and the mass change responses, it is concluded that during the electrodeposition, bismuth influences the structure of the PbO2 formed. Bi(III) also inhibits the oxidation of lead sulfate and affects the reduction kinetics of lead dioxide. During successive cyclization (aging), the presence of bismuth accelerates the hydration of PbO2. Keywords Lead dioxide . Lead-acid battery . EQCM . Bismuth additive
Introduction Porous lead dioxide materials are used in lead-acid batteries [1–4] as well as in many industrial applications such as wastewater treatment for oxidation of organic compounds [5–13]. The electrochemical behavior of pure lead dioxide layers (charge-discharge characteristics, aging processes) has been widely studied previously [14–19]. In order to improve the electrochemical and mechanical properties of PbO2 layers, several investigations have been carried out, e.g., by using different metals or metal oxides This paper is dedicated to the eminent scientist and erudite scholar Professor Fritz Scholz on the occasion of his 65th birthday with the appreciation of his pioneering work in the field of solid state electrochemistry and numerous other contributions to contemporary electrochemistry Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10008-020-04569-3) contains supplementary material, which is available to authorized users. * György Inzelt [email protected] Balázs Broda [email protected] 1
Department of Physical Chemistry, Institute of Chemistry, Eötvös Loránd University, Pázmány Péter sétány 1/A, Budapest 1117, Hungary
[20–22] including bismuth [23, 24]. However, the results and the explanations of some studies are confusing regarding to the effects of these additives on certain properties. In his review [25], Koop also stated that the published experimental evidences for both the perceived and actual effects of bismuth on lead-acid battery performance are complex and often contradictory. Therefore, it is evident that electrochemical studies combined with supplementary techniques are necessary to gain a deeper understanding of the complex behavior of PbO2 electrode doped with bismuth. The electrochemical quartz crystal microbalance (EQCM) is a powerful technique for monitorin
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