Abstract
In-situ spectroelectrochemical technique has been applied to investigate passivating surface film on porous carbon electrode and plasma enhanced chemical vapour deposited (PECVD) carbon film electrode in organic electrolytic solution consisting of ethylene carbonate (EC) and diethyl carbonate (DEC) solvent, and 1 M LiPF6 and LiAsF6. Water impurity with the concentration of 0 M, 0.02 M, 0.05 M, and 0.1 M H20 was added to 1 M LiPF6-EC/DEC solution. In-situ Fourier transform infra-red (FTIR) spectra of the surface film on both electrodes with the constituents of ROCO2Li, Li2CO3, and LixPFy suggested that the reduction of EC to ROCO2Li runs via a one-electron transfer pathway as a result of diffusion of water through the surface film, and then Li2CO3 formation proceeds simultaneously by the chemical reaction of ROCO2Li with water. From the measured potential dependence of the amount of the salt reduction products, it is suggested that the surface film formed in 1 M LiPF6EC/DEC solution gives a poorer passivity as compared with that formed in 1 M LiAsF6-EC/DEC solution, which is due to the considerable interference of LiPE6 salt reduction with the compact sedimentation of ROCO2Li on the electrode. In-situ FFIR spectra of the surface film showed that all the peak intensities of the three constituents significantly increase with increasing water content under application of the negative potentials with respect to open circuit potential (OCP). From these experimental results, the dependence of the passivity of the surface film on the carbon electrode on the water concentration of the electrolyte, as well as on the lithium salt type, was discussed in view of the salt and solvent reactivities.
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Pyun, SI. Compositional analysis of passivating surface film formed on carbon electrode in organic electrolytic solution using in-situ spectroelectrochemical technique. Metals and Materials 5, 101–108 (1999). https://doi.org/10.1007/BF03026010
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DOI: https://doi.org/10.1007/BF03026010