Electrochemical and structural properties of the electrical double layer of two-component electrolytes in response to varied electrode potential.

The electrochemical and structural properties of the electrical double layers for two-component electrolytes were studied by Monte Carlo simulations using simple models. When the electrolyte contains two species of cations that have different diameters, the capacitance on the cathode dramatically increases as a large negative potential is applied. This behavior is qualitatively similar to the one reported in an experimental work that has used Li-containing ionic liquid as the electrolyte [M. Yamagata et al., Electrochim. Acta 110, 181-190 (2013)], in which it has also been reported that addition of Li ions to the electrolyte enhances the potential window to the negative side. The analysis of the ionic structure showed that the electrical double layer on the cathode is dominantly formed by the larger cations under small negative potentials, while they are replaced by the smaller cations under large negative potentials. This transition of the ionic structure with electrode potential is also consistent with the enhancement of the potential window that was found in the experimental work, which suggests that the organic cations are expelled from the electrical double layer under large negative potentials and the chance of decomposition is reduced.

In situ Scanning Electron Microscopy of Silicon Anode Reactions in Lithium-Ion Batteries during Charge/Discharge Processes.

A comprehensive understanding of the charge/discharge behaviour of high-capacity anode active materials, e.g., Si and Li, is essential for the design and development of next-generation high-performance Li-based batteries. Here, we demonstrate the in situ scanning electron microscopy (in situ SEM) of Si anodes in a configuration analogous to actual lithium-ion batteries (LIBs) with an ionic liquid (IL) that is expected to be a functional LIB electrolyte in the future. We discovered that variations in the morphology of Si active materials during charge/discharge processes is strongly dependent on their size and shape. Even the diffusion of atomic Li into Si materials can be visualized using a back-scattering electron imaging technique. The electrode reactions were successfully recorded as video clips. This in situ SEM technique can simultaneously provide useful data on, for example, morphological variations and elemental distributions, as well as electrochemical data.

In situ SEM observation of the Si negative electrode reaction in an ionic-liquid-based lithium-ion secondary battery.

By exploiting characteristics such as negligible vapour pressure and ion-conductive nature of an ionic liquid (IL), we established an in situ scanning electron microscope (SEM) method to observe the electrode reaction in the IL-based Li-ion secondary battery (LIB). When 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide ([C2mim][FSA]) with lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) was used as the electrolyte, the Si negative electrode exhibited a clear morphology change during the charge process, without any solid electrolyte interphase (SEI) layer formation, while in the discharge process, the appearance was slightly changed, suggesting that a morphology change is irreversible in the charge-discharge process. On the other hand, the use of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][TFSA]) with Li[TFSA] did not induce a change in the Si negative electrode. It is interesting to note this distinct contrast, which could be attributed to SEI layer formation from the electrochemical breakdown of [C2mim](+) at the Si negative electrode|separator interface in the [C2mim][TFSA]-based LIB. This in situ SEM observation technique could reveal the effect of the IL species electron-microscopically on the Si negative electrode reaction.