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In-Situ Scanning Tunneling Microscopy and Electrochemical Quartz Crystal Microbalance Studies of the SEI Formation on Graphite Electrodes
In the mid-1990s M. Inaba et al. carried out a series of experiments about the SEI-formation on model graphite electrodes and the co-intercalation of Li+-ions together with their solvation shell using Electrochemical Scanning Tunneling Microscopy (EC-STM).5 EC-STM is a very powerful technique for surface studies, since it offers the possibility to in-situ image molecular processes at the electrode/electrolyte interface. In the present study, the SEI-formation was examined in depth by in-situ EC-STM on highly oriented pyrolytic graphite (HOPG) model electrodes both in commercial Li+-ion battery electrolytes as well as alternative electrolyte systems (see Figure 1). In addition, the Electrochemical Quartz Crystal Microbalance technique (EQCM) as another in-situ method gave further insights into the SEI-formation. Both in-situ techniques provided valuable information about the electrochemical characteristics of this system, leading to better understanding of the formation mechanism and the morphological appearance of the SEI.
Figure 1. In-Situ EC-STM study of the SEI-formation on HOPG in 1M LiPF6 in EC/DMC electrolyte: The surface is imaged while the potential (line) is scanned from 2.0 V vs. Li/Li+ to 1 V, held at this potential, and scanned back to 2 V. The y-axis of the STM image is converted to a time scale to correlate changes in morphology to the applied potential
1M. Armand, J.-M. Tarascon, Nature, 451 (2008) 652
2J. B. Goodenough, J. Solid State Electrochem, 16 (2012) 2019
3P. B. Balbuena, Y. Wang, Imperial College Press (2004), ISBN 1-86094-362-4
4H. Tavassol, J.W. Buthker, G.A. Ferguson, L.A. Curtiss, A.A. Gewirth, J. Electrochem. Soc., 159 (2012) A730-A738.
5M. Inaba, Z. Siroma, A. Funabiki, Z. Ogumi, T. Abe, Y. Mizutani, M. Asano, Langmuir, 19 (1996) 1535