In this discussion paper we discuss our recent results on the electrodeposition of materials and in situ STM/AFM measurements which demonstrate that ionic liquids should not be regarded as neutral solvents which all have similar properties. In particular, we focus on differences in interfacial structure (solvation layers) on metal electrodes as a function of ionic liquid species. Recent theoretical and experimental results show that conventional double layers do not form on metal electrodes in ionic liquid systems. Rather, a multilayer architecture is present, with the number of layers determined by the ionic liquid species and the properties of the surface; up to seven discrete interfacial solvent layers are present on electrode surfaces, consequently there is no simple electrochemical double layer. Both the electrodeposition of aluminium and of tantalum are strongly influenced by ionic liquids: in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]TFSA, aluminium is obtained as a nanomaterial, whereas in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]TFSA, a microcrystalline material is made. Tantalum can be deposited from [Py(1,4)]TFSA, whereas from [EMIm]TFSA only non-stoichiometric tantalum fluorides TaF(x) are obtained. It is likely that solvation layers influence these reactions.

Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc.

Ionic liquids are potential designer electrolytes for energy storage devices such as batteries and capacitors wherein by changing the cation and anion of the ionic liquid (IL) the solid/liquid interface can be tuned, thereby influencing the charge and mass transfer processes. In this paper, we show the influence of water on the electrified ionic liquid 1-ethyl-3-methyl­imidazolium trifluoro­methyl­sulfonate ([Emim]­TfO)/Au(111) interface using in situ atomic force microscopy (AFM) and spectroscopy. A clear “water in IL” to “IL in water” transition could be observed in the range of 20–30 vol % of water using vibrational spectroscopy. Above 30 vol % of water the cation–anion interaction in the ionic liquid drastically reduced, which was ascertained by both spectroscopy and interfacial studies using in situ AFM. In situ AFM results further revealed that the structure of the innermost (Stern) layer depends both on the applied electrode potential and the amount of added water. A transition from a multilayered structure to a classical double-layered structure occurred at −1.0 V on changing the water concentration from 30 to 50 vol %. Furthermore, the morphology of the electrodeposited Zn could be altered with addition of water to the electrolyte which has some potential for Zn-based batteries.

Ionic liquids (ILs) form a multilayered structure at the solid/electrolyte interface, and the addition of solutes can alter it. For this purpose, we have investigated the influence of the silver bis(trifluoromethylsulfonyl)amide (AgTFSA) concentration in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py]TFSA) on the layering using in situ atomic force microscopy. AFM investigations revealed that the Au(111)/electrolyte interface indeed depends on the concentration of the salt where a typical " IL" multilayered structure is retained only at quite low concentrations of the silver salt (e.g. ≤200 μM). However, at 200 μM AgTFSA/[Py]TFSA and above this "IL" multilayered structure is disturbed/varied. A simple double layer structure was observed at 500 μM AgTFSA in [Py]TFSA. Furthermore, the widths of the innermost layers have been found to be dependent on the concentration and on the applied electrode potentials. Our AFM results show that the concentration of solutes strongly influences the structure of the electrode/electrolyte interface and can provide new insights into the electrical double layer structure of the electrode/ionic liquid interface. We also introduce a semi-continuum theory to discuss the double layer structure.

In this paper, the NaFSI-[Py 1,4 ]FSI/Au(111) interface was investigated using cyclic voltammetry (CV) and in situ atomic force microscopy (AFM). Raman spectroscopy was used to evaluate the Na + solvation in [Py 1,4 ]FSI. It was found that Na coordinates with three FSIforming [Na(FSI) 3 ] 2-. In situ AFM revealed that the interaction of [Py 1,4 ]FSI with Au (111) is much stronger compared to other ionic liquids measured using the same technique. On applying a potential, a force of about 50 nN is required to penetrate through the innermost layer. On addition of low concentration of NaFSI (0.05 M), an insignificant change in the innermost solvation layer was observed, whereas on addition of 0.25 M and 0.5 M NaFSI, a significant change in the interfacial structure was noted. The present study clearly shows that Na + ions vary the ionic liquid/Au(111) interface and could provide insight into the interfacial processes in ionic liquid based sodium batteries.

The highly ordered pyrolytic graphite ( H O P G ) / 1 -o c t y l -3 -m e t h y l i m i d a z o l i u m b i s -(trifluoromethylsulfonyl)imide ([OMIm]Tf 2 N) interface is examined by ultrahigh vacuum scanning tunneling microscopy (UHV-STM), atomic force microscopy (UHV-AFM) (and as a function of potential by in situ scanning tunneling microscopy (STM)), in situ atomic force microscopy (AFM), and density functional theory (DFT) calculations. In situ STM and AFM results reveal that multiple ionic liquid (IL) layers are present at the HOPG/electrode interface at all potentials. At open-circuit potential (OCP), attractions between the cation alkyl chain and the HOPG surface result in the ion layer bound to the surface being cation rich. As the potential is varied, the relative concentrations of cations and anions in the surface layer change: as the potential is made more positive, anions are preferentially adsorbed at the surface, while at negative potentials the surface layer is cation rich. At −2 V an unusual overstructure forms. STM images and AFM friction force microscopy measurements both confirm that the roughness of this overstructure increases with time. DFT calculations reveal that [OMIm] + is attracted to the graphite surface at OCP; however, adsorption is enhanced at negative potentials due to favorable electrostatic interactions, and at −2 V the surface layer is cation rich and strongly bound. The energetically most favorable orientation within this layer is with the [OMIm] + octyl chains aligned "epitaxially" along the graphitic lattice. This induces quasi-crystallization of cations on the graphite surface and formation of the overstructure. An alternative explanation may be that, because of the bulkiness of the cation sitting along the surface, a single layer of cations is unable to quench the surface potential, so a second layer forms. The most energetically favorable way to do this might be in a quasi-crystalline/multilayered fashion. It could also be a combination of strong surface binding/orientations and the need for multilayers to quench the charge.

No abstract

No abstract