New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer.

Slow and fast capacitive process taking place at the ionic liquid/electrode interface.

Electrochemical impedance spectroscopy was used to characterise the interface between the ultrapure room temperature ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and a Au(111) working electrode at electrode potentials more positive than the open circuit potential (-0.14 V vs. Pt pseudo-reference). Plots of the potential-dependent data in the complex capacitance plane reveal the existence of a fast and a slow capacitive process. In order to derive the contribution of both processes to the overall capacitance, the complex capacitance data were fitted using an empirical Cole-Cole equation. The differential capacitance of the fast process is almost constant between -0.14 V and +0.2 V (vs. Pt pseudo-reference) and decreases at more positive potentials, while the differential capacitance of the slower process exhibits a maximum at +0.2 V. This maximum leads to a maximum in the overall differential capacitance. We attribute the slow process to charge redistributions in the innermost ion layer, which require an activation energy in excess of that for ion transport in the room temperature ionic liquid. The differential capacitance maximum of the slow process at +0.2 V is most likely caused by reorientations of the 1-butyl-1l-methylpyrrolidinium cations in the innermost layer with the positively charged ring moving away from the Au(111) surface and leaving behind voids which are then occupied by anions. In a recent Monte Carlo simulation by Federov, Georgi and Kornyshev (Electrochem. Commun. 2010, 12, 296), such a process was identified as the origin of a differential capacitance maximum in the anodic regime. Our results suggest that the time scales of capacitive processes at the ionic liquid/metal interface are an important piece of information and should be considered in more detail in future experimental and theoretical studies.

An in situ STM/AFM and impedance spectroscopy study of the extremely pure 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate/Au(111) interface: potential dependent solvation layers and the herringbone reconstruction.

The structure and dynamics of the interfacial layers between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy measurements. The in situ scanning tunnelling microscopy measurements reveal that the Au(111) surface undergoes a reconstruction, and at -1.2 V versus Pt quasi-reference the famous (22 × âˆš3) herringbone superstructure is probed. Atomic force microscopy measurements show that multiple ion pair layers are present at the ionic liquid/Au interface which are dependent on the electrode potential. Upon applying cathodic electrode potentials, stronger ionic liquid near surface structure is detected: both the number of near surface layers and the force required to rupture these layers increases. The electrochemical impedance spectroscopy results reveal that three distinct processes take place at the interface. The fastest process is capacitive in its low-frequency limit and is identified with electrochemical double layer formation. The differential electrochemical double layer capacitance exhibits a local maximum at -0.2 V versus Pt quasi-reference, which is most likely caused by changes in the orientation of cations in the innermost layer. In the potential range between -0.84 V and -1.04 V, a second capacitive process is observed which is slower than electrochemical double layer formation. This process seems to be related to the herringbone reconstruction. In the frequency range below 1 Hz, the onset of an ultraslow faradaic process is found. This process becomes faster when the electrode potential is shifted to more negative potentials.