Understanding the electrode-electrolyte interface is essential in the battery research as the ion transport and ion structures at the interface most likely affect the performance of a battery. Here we investigate interfacial structures of three ionic liquids: 1-ethyl-3-methylimidazolium dicyanamide ([Cmim][dca]), 1-butyl-3-methylimidazolium dicyanamide ([Cmim][dca]) and N-butyl-N-methylpyrrolidinium dicyanamide ([Cmyr][dca]) at a charged and uncharged graphene interface using molecular dynamics simulations. We find that these ionic liquids (ILs) behave differently both in the bulk phase and near a graphene interface and we find that this difference is apparent in all types of analyses performed here. First, a partial density analysis in the direction perpendicular to the surface of the electrodes, which, in the cases near a negatively charged graphene, reveals that the pyrrolidinium system is generally more layered than the imidazolium systems. Second, a 2D topographic structure analysis of the IL species in the inner layer near a negatively charged graphene surface, which reveals that the pyrrolidinium system exhibits a quasi-hexagonal surface configuration of the cations, while the imidazolium systems show linearly arranged groups of cations. Third, a 3D orientation-preference analysis of cation rings near the negative graphene electrode, which shows that the pyrrolidinium rings prefer to lie parallel to the electrode surface while the imidazolium rings prefer to stand on the electrode surface at high tilt angles. Extending the imidazolium alkyl chain was found to reduce the number of imidazoliums that can link up into linearly arranged groups in the inner layer 2D structures. Our results support earlier experimental findings and indicate that the interfacial nanostructures may have a significant influence on the electrochemical performance of IL-based batteries.

The latest advances in the stabilization of Li/Na metal battery and Li-ion battery cycling has highlighted the importance of electrode/electrolyte interface (Solid Electrolyte Interphase -SEI) and its direct link to cycling behaviour. In order to understand the structure and properties of the SEI, we used combined experimental and computational studies to unveil how the ionic liquid (IL) cation nature and salt concentration impact the silicon/IL electrolyte interfacial structure and the formed SEI. The nature of IL cation is found to be important to control the electrolyte reductive decomposition that influences the SEI composition and properties, and the reversibility of the Li-Si alloying process. Also, increasing the Li salt concentration changes the interface structure for a favorable and less resistive SEI. The most promising interface for the Si-based battery was found to be in P 1222 FSI with 3.2 m LiFSI which leads to an optimal SEI after 100 cycles in which LiF and trapped LiFSI are the only distinguishable lithiated and fluorinated products detected. This study shows a clear link between the nano-structure of the IL electrolyte near the electrode surface, the resulting SEI, and the Si negative electrode cycling performance. More importantly, this work will aid rational design of Si-based Li-ion batteries using IL electrolytes in an area that has so far been neglected, reinforcing the benefits of superconcentrated electrolyte systems.

The electrochemical systems containing zinc dicyanamide salt (Zn(dca)) in both 1-ethyl-3-methylimidazolium dicyanamide ([Cmim][dca]) and N-butyl-N-methylpyrrolidinium dicyanamide ([Cmpyr][dca]) ionic liquids (ILs) have been studied by atomic force microscopy (AFM) on a highly oriented pyrolytic graphite (HOPG) surface under different conditions and applied potentials. The results reveal the following: (1) interfacial layers exist in both ILs, even after the addition of 3 wt% water and 9 mol% Zn(dca) salt. (2) The number of layers is different for the different ILs, with the [Cmim][dca]-based samples exhibiting a much more limited interfacial structure compared to the [Cmpyr][dca] at almost all of the tested conditions. (3) For the [Cmpyr][dca]-based samples, without added zinc salt, the number of detected interfacial layers increases with negative potential. With added zinc, the [Cmpyr][dca] sample shows about the same number of layers independent of the applied potentials, namely between 5-7. Likewise, for the [Cmim][dca] samples, with the zinc added the sample shows the same number of layers at the applied potentials, but for this system only 1-2 layers are detected. And (4) the addition of Zn(dca) into the [Cmim][dca] IL does not cause a large change in the interfacial ordering, whereas the addition of the same salt into the [Cmpyr][dca] samples is marked by a stark increase in both the number and the consistency of the perceived interfacial layers. These results are significant because they show a marked difference in the interfacial nanostructure between two zinc-based electrochemical systems that were previously shown to have distinctly different electrochemical behaviour, despite their chemical similarity.