It is well known that ethylene carbonate is compatible with graphite anode because a good SEI layer, which prevents the cointercalation of solvents into the graphite, is formed. In contrast, the cointercalation of solvents with Li+ into graphite takes place in other common solvents such as propylene carbonate (PC) and ethers, causing destruction of the graphite crystalline structure. However, it was reported that cointercalation of these solvents, namely, PC, dimethoxy ethane, and other solvents into graphite anode can be inhibited by increasing the Li salt concentration and intercalation of Li+ into graphite anode occurs reversibly.[4] We also observed the reversible Li+ intercalation/de-intercalation reaction in extremely concentrated G3-Li[TFSA] solution, although the cointercalation takes place in the solution containing excess G3 (Figure 3).[5] The electrode potential for the formation of Li+ intercalated graphite (including desolvation process of [Li(G3)]+) is expected to increase greatly against the Li salt concentration as well as the aforementioned potential of Li/Li+, because the potential depends on the activity of not only solvate cation but also free solvent. On the other hand, the electrode potential for cointercalation depends on only the activity of solvate cation, since the reaction does not include desolvation process. Thus, in the highly concentrated region, the activity of free solvent is very small, and the electrode potential for Li-intercalated graphite formation is higher than that for cointercalation, leading to the suppression of cointercalation. In this study, it was revealed that the activity of the solvent in an electrolyte should be a key factor in controlling electrochemical reaction. Detail discussion of the relationship between the activity of free solvent and electrochemical reaction will be reported.
Acknowledgement
This study was supported in part by the ALCA program of the Japan Science and Technology Agency, and by the Technology Research Grant Program of NEDO, for which the authors are grateful.
References
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