Journal of the Electrochemical Society, Vol.143, No.8, 2548-2558, 1996
Electrochemical Oxidation Processes on Ni Electrodes in Propylene Carbonate Containing Various Electrolyte Salts
Electrochemical oxidation processes on Ni electrodes in propylene carbonate electrolytes were investigated by using cyclic voltammetry, x-ray photoelectron spectroscopy, and in situ Fourier transform infrared spectroscopy. The results of these analyses suggest that Ni electrodes, electrolyte salts, and solvent are oxidized at a greater anodic potential than 4.2 V vs. Li/Li+. When propylene carbonate (PC) electrolyte containing LiAsF6, LiBF4, or LiPF6 was used, a large amount of Ni fluorides and oxides formed on the Ni electrodes and became inactive in response to Ni oxidation. The Fourier transform infrared measurement showed that the oxidation of PC in these electrolytes is enhanced by the formation of the above-mentioned Ni compounds in the first scan. On the ether hand, inactivation was not observed for PC electrolytes containing LiCF3SO3. Correspondingly, the oxidation of PC in this electrolyte was more suppressed than that in the other three electrolytes. When PC containing LiClO4 was used as an electrolyte, the formation of Ni oxides was observed as well as the active oxidation of PC. This result indicates that Ni oxides are actively involved in the electrochemical oxidation of PC. Thus, electrochemical oxidation processes on Ni electrodes in various PC electrolytes can be explained by the oxidation of Ni. electrodes in association with anion decomposition, which determines a type of products formed on Ni electrodes.
Keywords:TRANSFORM INFRARED-SPECTROSCOPY;IN-SITU;CYCLING EFFICIENCY;LITHIUM;SURFACE;MONOXIDE;FILMS;SPECTROELECTROCHEMISTRY;POTENTIALS;ADSORPTION