Mesostructure and physical properties of aqueous mixtures of the ionic liquid 1-ethyl-3-methyl imidazolium octyl sulfate doped with divalent sulfate salts in the liquid and the mesomorphic states.

This paper extends the study of the induced temperature change in the mesostructure and in the physical properties occurring in aqueous mixtures of the ionic liquid 1-ethyl-3-methyl imidazolium octyl-sulfate [EMIm][OSO4]. For some compositions, these mixtures undergo a phase transition between the liquid (isotropic in the mesoscale) and the mesomorphic state (lyotropic liquid crystalline) at about room temperature. The behavior of mixtures doped with a divalent metal sulfate was investigated in order to observe their applicability as electrolytes. Calcium sulfate salt is almost insoluble even in the 20 wt% water mixture. The magnesium salt, in contrast, can be dissolved up to concentrations of 730 ppm in the same mixture and it has a profound impact on its properties. Six aqueous mixtures (with water content from 10 wt% to 33 wt%) of [EMIm][OSO4] were saturated with magnesium sulfate salt, producing the ternary mixture [EMIm][OSO4] + H2O + MgSO4. Viscosity, density and ionic conductivity for these samples were measured from 10 °C to 90 °C. In addition, SAXS, FTIR, diffussion NMR and Raman spectroscopy of the most interesting samples have been performed, and structural data indicate a transition between a hexagonal lyotropic liquid crystalline phase below and an isotropic solution phase above room temperature. The octyl sulfate anions of the cylindrical micelles in the hexagonal phase are coordinated with water molecules through H-bonds (about four per sulfate anion), while the [EMIm] cations seem to be poorly coordinated and so free to move. Inorganic salt addition reinforces that network, increasing the phase transition temperature.

Stability of nicotinate and dodecyl sulfate in a Lewis acidic ionic liquid for aluminum electroplating and characterization of their degradation products.

Plating bath additives are essential for optimization of the morphology of electroplated layers. The ionic liquid 1-ethyl-3-methylimidazolium (EMIM) chloride plus 1.5 mol equivalents of AlCl3 has great potential for electroplating of aluminum. In this study, the chemical and electrochemical stability of the additives EMIM-nicotinate and sodium dodecyl sulfate and their effect on the stability of EMIM was investigated and analyzed. Nicotinate and its electrochemical decomposition product ß-picoline could be detected and we show with a single HPLC-UV-MS method that EMIM is not affected by the decomposition of this additive. An adapted standard HPLC-UV-MS method together with GC-MS and ion chromatography was used to analyze the decomposition products of SDS and possible realkylation products of EMIM. Several volatile medium and short chain-length alkanes as well as sulfate ions have been found as decomposition products of SDS. Alkenium ions formed as intermediates during the decomposition of SDS realkylate EMIM to produce mono- up to pentasubstituted alkyl-imidazoles. A reaction pathway involving Wagner-Meerwein rearrangements and Friedel-Crafts alkylations has been suggested to account for the formation of the detected products.

In situ PM-IRRAS of a glassy carbon electrode/deep eutectic solvent interface.

The interface of a 1 : 2 molar choline chloride/ethylene glycol deep eutectic solvent with a glassy carbon electrode has been investigated by polarization modulation reflection-absorption spectroscopy (PM-IRRAS). Temporal spectral changes at open circuit potential show the experiments to be surface sensitive and indicate slow adsorption of electrolyte molecules on the electrode surface. In situ spectroelectrochemical PM-IRRAS measurements reveal characteristic potential-dependent changes of band intensities and wavenumber-shifts in the surface spectra. The potential dependent spectral changes are discussed in terms of adsorption, reduction, desorption and reorientation of choline cations at the interface. Analogies are drawn to the ionic layer structure proposed for the architecture of electrode/ionic liquid interfaces. The results show that in situ PM-IRRAS is generally applicable to glassy carbon electrodes and to electrode interfaces with deep eutectic solvents.

Separation of 1,3-substituted imidazoles for quality control of a Lewis acidic ionic liquid for aluminum electroplating.

Ionic liquids (ILs) are already used or have great potential in many industrial applications. Knowledge about their unique physicochemical characteristics makes ILs suitable for the electrodeposition of metals with very low negative potentials. Aluminum with its good corrosion protection behavior has great capability to be electroplated from IL electrolytes on steel substrates. The stability of the chosen electrolyte is very important to ensure industrial applicability. In this study, temperature and electrochemical long-term stability from electrolytes based on a Lewis acidic mixture of AlCl3 and 1-ethyl-3-methylimidazolium chloride are investigated. A published method was modified to identify possible degradation products using mass spectrometric detection. The optimized method used an Agilent Zorbax SB-Phenyl column (2.0 × 150 mm, 5 µm particles) with a 20 mmol TFA and 5% ACN mobile phase. This method allowed the quantification of several imidazoles from 0.1 to 100 mg/L. When analyzing the long-term stressed electrolytes, no significant changes in electrolyte composition could be observed.

Electrochemical current-sensing atomic force microscopy in conductive solutions.

Insulated atomic force microscopy probes carrying gold conductive tips were fabricated and employed as bifunctional force and current sensors in electrolyte solutions under electrochemical potential control. The application of the probes for current-sensing imaging, force and current-distance spectroscopy as well as scanning electrochemical microscopy experiments was demonstrated.

Monitoring of Pore Orientation by in Operando Grazing Incidence Small-Angle X-ray Scattering during Templated Electrodeposition of Mesoporous Pt Films.

We have used in operando grazing incidence small-angle X-ray scattering (GISAXS) to monitor structural changes during templated electrodeposition of mesoporous platinum films on gold electrodes from a ternary lyotropic liquid crystalline mixture of aqueous hexachloroplatinic acid and the diblock copolymer surfactant Brij56. While the cylindrical micelles of the lyotropic liquid crystal (LLC) in the hexagonal phase have a center-to-center distance of 7.5 nm with a preferential alignment parallel to the electrode surface, the electrodeposited platinum films contain highly ordered mesopores arranged in a 2D hexagonal structure, with a center-to-center distance of about 8.5 nm and a preferential orientation perpendicular to the electrode surface. The progression of structural changes of the LLC template and the deposited mesoporous Pt could be monitored for the first time in operando by GISAXS: within the first 14 s of deposition, a nucleation burst of Pt coincides with a loss of preferential alignment of the LLC. Initially, the morphology of the 2-dimensionally nucleated Pt replicates the Au substrate. During the following 5 to 7 min, the growth morphology of the Pt film changes, and vertically aligned mesopores form. Our results indicate mutual interaction between the species involved in the electrodeposition and the LLC template, leading to a partial loss of horizontal orientation of the LLC during Pt nucleation before vertical rearrangement of the micelles to the electrode surface. The vertically aligned mesopores in the Pt and the possibility to produce freestanding films make these materials interesting in fields such as electrocatalysis, energy harvesting, and nanofluidics.

Corrosion of Passive Aluminum Anodes in a Chloroaluminate Deep Eutectic Solvent for Secondary Batteries: The Bad, the Good, and the Ugly.

The passivity of aluminum is detrimental to its performance as an anode in batteries. Soaking of native oxide-covered aluminum in a chloroaluminate deep eutectic solvent gradually activates the electrode surface, which is reflected in a continuously decreasing open circuit potential. The underlying processes were studied by analyzing the 3 to 7 nm thick layer of native oxide after increasing periods of soaking with secondary neutral mass spectrometry, X-ray photoelectron spectroscopy, and energy-dispersive spectroscopy in a transmission electron microscope. They consistently show permeation of electrolyte species into the layer associated with gradual swelling. After extended periods of soaking at open circuit potentials, local deposits of a range of foreign metals have been found in scanning electron microscopy images of the electrode surface. The pitting corrosion is caused by trace metal ion impurities present in the electrolyte and results in highly nonuniform current density distribution during discharge/charge cycling of battery cells as shown by local deposits of aluminum. The processes during soaking at open circuit potentials have been monitored by electrochemical impedance spectroscopy and could be analyzed by fitting an equivalent circuit model for pitting corrosion.

Impact of Iodine Electrodeposition on Nanoporous Carbon Electrode Determined by EQCM, XPS and In Situ Raman Spectroscopy.

The charging of nanoporous carbon via electrodeposition of solid iodine from iodide-based electrolyte is an efficient and ecofriendly method to produce battery cathodes. Here, the interactions at the carbon/iodine interface from first contact with the aqueous electrolyte to the electrochemical polarization conditions in a hybrid cell are investigated by a combination of in situ and ex situ methods. EQCM investigations confirm the flushing out of water from the pores during iodine formation at the positive electrode. XPS of the carbon surface shows irreversible oxidation at the initial electrolyte immersion and to a larger extent during the first few charge/discharge cycles. This leads to the creation of functional groups at the surface while further reactive sites are consumed by iodine, causing a kind of passivation during a stable cycling regime. Two sources of carbon electrode structural modifications during iodine formation in the nanopores have been revealed by in situ Raman spectroscopy, (i) charge transfer and (ii) mechanical strain, both causing reversible changes and thus preventing performance deterioration during the long-term cycling of energy storage devices that use iodine-charged carbon electrodes.

Preparation of CoNi high surface area porous foams by substrate controlled electrodeposition.

We demonstrate that nanofabrication of 3D dendritic CoNi alloy foams with an open porous structure can be achieved by electrodeposition onto a single-crystalline Cu(111) substrate at ambient conditions. The very low wettability of this substrate caused by its low surface energy allows tailoring the CoNi deposit morphology. This is concluded from a comparison of polycrystalline Cu substrates with single-crystalline ones of different orientations. The advantages of the present CoNi alloy foams are low internal stresses and good mechanical stability on the substrate. In a second step, by comparing the catalytic properties of the achieved foam with those of CoNi layers obtained on polycrystalline Cu substrates, it is shown that the morphology of the CoNi layers has a decisive influence on the kinetics of the surface redox reaction. The higher reaction rate makes the open foam suitable as catalyst for oxygen evolution in electrolysers. The reversibility of the redox process provides great potential for the achieved porous layers to be used as positive material in alkaline batteries.

Atomic force microscopy-scanning electrochemical microscopy: influence of tip geometry and insulation defects on diffusion controlled currents at conical electrodes.

Numerical simulations were performed to predict the amperometric response of conical electrodes used as atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) probes. A simple general expression was derived which predicts their steady state limiting current as a function of their insulation sheath thickness and cone aspect ratio. Simulated currents were successfully compared with experimental currents. Geometrical parameters such as insulation angle and tip bluntness were then studied to determine their effect on the limiting current. Typical tip defects were also modeled using 3D simulations, and their influence on the current was quantified. Although obtained for SECM-AFM probes, these results are directly applicable to conical micro- and nanoelectrodes.

Persistent and reversible solid iodine electrodeposition in nanoporous carbons.

Aqueous iodine based electrochemical energy storage is considered a potential candidate to improve sustainability and performance of current battery and supercapacitor technology. It harnesses the redox activity of iodide, iodine, and polyiodide species in the confined geometry of nanoporous carbon electrodes. However, current descriptions of the electrochemical reaction mechanism to interconvert these species are elusive. Here we show that electrochemical oxidation of iodide in nanoporous carbons forms persistent solid iodine deposits. Confinement slows down dissolution into triiodide and pentaiodide, responsible for otherwise significant self-discharge via shuttling. The main tools for these insights are in situ Raman spectroscopy and in situ small and wide-angle X-ray scattering (in situ SAXS/WAXS). In situ Raman confirms the reversible formation of triiodide and pentaiodide. In situ SAXS/WAXS indicates remarkable amounts of solid iodine deposited in the carbon nanopores. Combined with stochastic modeling, in situ SAXS allows quantifying the solid iodine volume fraction and visualizing the iodine structure on 3D lattice models at the sub-nanometer scale. Based on the derived mechanism, we demonstrate strategies for improved iodine pore filling capacity and prevention of self-discharge, applicable to hybrid supercapacitors and batteries.

Author Correction: Persistent and reversible solid iodine electrodeposition in nanoporous carbons.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Electrochemical Behavior of Graphene in a Deep Eutectic Solvent.

Graphene electrodes and deep eutectic solvents (DESs) are two emerging material systems that have individually shown highly promising properties in electrochemical applications. To date, however, it has not been tested whether the combination of graphene and DESs can yield synergistic effects in electrochemistry. We therefore study the electrochemical behavior of a defined graphene monolayer of centimeter-scale, which was produced by chemical vapor deposition and transferred onto insulating SiO2/Si supports, in the common DES choline chloride/ethylene glycol (12CE) under typical electrochemical conditions. We measure the graphene potential window in 12CE and estimate the apparent electron transfer kinetics of an outer-sphere redox couple. We further explore the applicability of the 12CE electrolyte to fabricate nanostructured metal (Zn) and metalloid (Ge) hybrids with graphene by electrodeposition. By comparing our graphene electrodes with common bulk glassy carbon electrodes, a key finding we make is that the two-dimensional nature of the graphene electrodes has a clear impact on DES-based electrochemistry. Thereby, we provide a first framework toward rational optimization of graphene-DES systems for electrochemical applications.

Reduced Faradaic Contributions and Fast Charging of Nanoporous Carbon Electrodes in a Concentrated Sodium Nitrate Aqueous Electrolyte for Supercapacitors.

The Faradaic processes related to electrochemical water reduction at the nanoporous carbon electrode under negative polarization are reduced when the concentration of aqueous sodium nitrate (NaNO3) is increased or the temperature is decreased. This effect enhances the relative contribution of ion electrosorption to the total charge storage process. Hydrogen chemisorption is reduced in aqueous 8.0 m NaNO3 due to the low degree of hydration of the Na+ cation; consequently, less free water is available for redox contributions, driving the system to exhibit electrical double-layer capacitive characteristics. Hydrogen adsorption/desorption is facilitated in 1.0 m NaNO3 due to the high molar ratio. The excess of water shifts the local pH in carbon nanopores to neutral values, giving rise to a high overpotential for dihydrogen evolution in the latter. The dilution effect on local pH shift in 1.0 m NaNO3 can be reduced by decreasing the temperature. A symmetric activated carbon cell assembled with 8.0 m NaNO3 exhibits a high capacitance and coulombic efficiency, a larger contribution of ion electrosorption to the overall charge storage process, and a stable capacitance performance at 1.6 V.

Immobilization of Polyiodide Redox Species in Porous Carbon for Battery-Like Electrodes in Eco-Friendly Hybrid Electrochemical Capacitors.

Hybrid electrochemical capacitors have emerged as attractive energy storage option, which perfectly fill the gap between electric double-layer capacitors (EDLCs) and batteries, combining in one device the high power of the former and the high energy of the latter. We show that the charging characteristics of the positive carbon electrode are transformed to behave like a battery operating at nearly constant potential after it is polarized in aqueous iodide electrolyte (1 mol L-1 NaI). Thermogravimetric analysis of the positive carbon electrode confirms the decomposition of iodides trapped inside the carbon pores in a wide temperature range from 190 °C to 425 °C, while Raman spectra of the positive electrode show characteristic peaks of I3- and I5- at 110 and 160 cm-1, respectively. After entrapment of polyiodides in the carbon pores by polarization in 1 mol L-1 NaI, the positive electrode retains the battery-like behavior in another cell, where it is coupled with a carbon-based negative electrode in aqueous NaNO3 electrolyte without any redox species. This new cell (the iodide-ion capacitor) demonstrates the charging characteristics of a hybrid capacitor with capacitance values comparable to the one using 1 mol L-1 NaI. The constant capacitance profile of the new hybrid cell in aqueous NaNO3 for 5000 galvanostatic charge/discharge cycles at 0.5 A g-1 shows that iodide species are confined to the positive battery-like electrode exhibiting negligible potential decay during self-discharge tests, and their shuttling to the negative electrode is prevented in this system.

Virtual Issue: Advances in Electrochemistry.

Advances in Electrochemistry! This Virtual Issue on Advances in Electrochemistry highlights the rich diversity in the exciting and dynamic field of electrochemistry.

Tin, Bismuth, and Tin-Bismuth Alloy Electrodeposition from Chlorometalate Salts in Deep Eutectic Solvents.

The electrodeposition of tin, bismuth, and tin-bismuth alloys from SnII and BiIII chlorometalate salts in the choline chloride/ethylene glycol (1:2 molar ratio) deep eutectic solvent was studied on glassy carbon and gold by cyclic voltammetry, rotating disc voltammetry, and chronoamperometry. The SnII-containing electrolyte showed one voltammetric redox process corresponding to SnII/Sn0. The diffusion coefficient of [SnCl3]-, detected as the dominating species by Raman spectroscopy, was determined from Levich and Cottrell analyses. The BiIII-containing electrolyte showed two voltammetric reduction processes, both attributed to BiIII/Bi0. Dimensionless current/time transients revealed that the electrodeposition of both Sn and Bi on glassy carbon proceeded by 3D-progressive nucleation at a low overpotential and changed to instantaneous at higher overpotentials. The nucleation rate of Bi on glassy carbon was considerably smaller than that of Sn. Elemental Sn and Bi were electrodeposited on Au-coated glass slides from their respective salt solutions, as were Sn-Bi alloys from a 2:1 SnII/BiIII solution. The biphasic Sn-Bi alloys changed from a Bi-rich composition to a Sn-rich composition by making the deposition potential more negative.