Search Results (7)

The solid electrolyte interphase (SEI) on the anode of lithium-ion batteries (LIBs) has been studied thoroughly due to its crucial importance to the battery’s long-term performance. At the same time, most studies of the SEI apply ex situ characterization methods, which may introduce artifacts or misinterpretations as they do not investigate the SEI in its unaltered state immersed in liquid battery electrolyte. Thus, in this work, we focus on using the non-destructive combination of electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and impedance spectroscopy (EIS) in the same electrochemical cell. EQCM-D can not only probe the solidified products of the SEI but also allows for the monitoring of viscoelastic layers and viscosity changes of the electrolyte at the interphase during the SEI formation. EIS complements those results by providing electrochemical properties of the formed interphase. Our results highlight substantial differences in the physical and electrochemical properties between the SEI formed on copper and on amorphous carbon and show how formation parameters and the additive vinylene carbonate (VC) influence their growth. The EQCM-D results show consistently that much thicker SEIs are formed on carbon substrates in comparison to copper substrates. Full article

Its crucial importance to the long-term operation of lithium-ion batteries has made the solid electrolyte interphase (SEI) the subject of intensive research efforts. These investigations are challenging, however, due to the very complex and fragile nature of this layer. With its typical thickness being in the range of some 10 nm and its chemical make-up being highly sensitive to even the smallest amounts of impurities, it becomes clear that artifacts are easily introduced in investigations of the SEI, especially if the measurements are performed ex situ. To help ameliorate these issues, we herein report a combination of non-destructive operando techniques that can be employed simultaneously in the same electrochemical cell to provide a plethora of physical, morphological, and electrochemical data on the macroscopic and microscopic scale. These techniques encompass atomic force microscopy (AFM), electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D), and impedance spectroscopy (EIS). This work focuses on how to combine these techniques in a single electrochemical cell, which is suitable to study SEI formation while avoiding noise, crosstalk, inhomogeneous SEI formation, and other pitfalls. Full article

All-iron redox-flow batteries (AIRFB) are capable of addressing the needs for cost-effective long-term storage of renewable energies. Currently, a major limitation of AIRFB performance is the half-cell reaction of the anolyte utilising the redox couple Fe/Fe²⁺. In this work, the performance of sulphate and chloride-based iron electrolytes was investigated by combining cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM). The investigations demonstrate that complexing agents exert a detrimental influence on the kinetics of plating/stripping reactions, resulting in diffusivity reduction, while favouring hydrogen evolution reaction (HER). The coulombic (plating) efficiency was found to be 87.1% at −1.2 V vs. Ag/AgCl (sat’d) at pH 3.5, while the coulombic efficiency in oxidation sweep (stripping) was observed to be 100% in an electrolyte containing 0.8 M FeCl₂ and 3 M NH₄Cl. In the context of iron deposition, the most crucial factors are the suppression of HER, and the influence of diffusion limitations, as well as the role of additives in this process to achieve a high reversibility. It is evident that the investigated complexing agents of glycine, malic acid and malonic acid are inadequate for battery-compatible, efficient properties, given that the overvoltages for the charge transfer reaction are too high and parasitic HER reduces coulombic efficiencies. Ultimately, the choice of deposition parameters from EQCM and electrolyte composition reduced to 0.8 M FeCl₂, and 3 M NH₄Cl can optimise the battery efficiencies as such. Full article

Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD^1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF₆ and working in TBAClO₄ and TBABF₄. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films. Full article

In this research, a model for electrodeposition of zinc oxide (ZnO) nanostructures over indium-doped tin-oxide (ITO) glass using pulsed current and zinc chloride as source of zinc was proposed. For the model, reactions kinetics rate constants were evaluated by obtaining the reaction product solid mass of the various species through time using an electrochemical quartz crystal microbalance (EQCM). To obtain a mathematical model of the electrodeposition using Ansys CFX 2D simulation software, the reaction kinetics rates were used to calculate mass transfer in the volume closest to the surface. The model was applied to the experimental electrodeposition conditions to validate its accuracy. Dense wurtzite nanostructures with controlled morphology were obtained on a indium-doped tin-oxide (ITO) glass. Sample characterization was performed using high-resolution field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) on focused ion beam milled (FIBed) sheets from wurtzite mono-crystals. Average crystallite size was evaluated by X-ray diffraction (XRD) using the Scherrer equation, and superficial areas were evaluated by Brunauer, Emmett, and Teller (BET) method. Through the experimental results, a chemical model was developed for the competing reactions based on the speciation of zinc considering pH evolution, and kinetic constants, on the oxygen rich aqueous environment. Owing to the model, an accurate prediction of thickness and type of electrodeposited layers, under given conditions, is achieved. This allows an excellent control of the optical properties of Wurtzite as a photon absorber, for an efficient separation of the electron-hole pair for conduction of the electric charges formed. The large surface area, and small wurtzite crystallites evenly distributed on the thin film electrodeposited over the ITO conductive layer are promising features for later dye-sensitized photovoltaic cell production. Full article

The response of the quartz crystal microbalance (QCM, also: QCM-D for “QCM with Dissipation monitoring”) to loading with a diverse set of samples is reviewed in a consistent frame. After a brief introduction to the advanced QCMs, the governing equation (the small-load approximation) is derived. Planar films and adsorbates are modeled based on the acoustic multilayer formalism. In liquid environments, viscoelastic spectroscopy and high-frequency rheology are possible, even on layers with a thickness in the monolayer range. For particulate samples, the contact stiffness can be derived. Because the stress at the contact is large, the force is not always proportional to the displacement. Nonlinear effects are observed, leading to a dependence of the resonance frequency and the resonance bandwidth on the amplitude of oscillation. Partial slip, in particular, can be studied in detail. Advanced topics include structured samples and the extension of the small-load approximation to its tensorial version. Full article

The critical role of divalent ions (M²⁺) in the self-assembly of SbpA S-layer proteins (from Lysinibacillus sphaericus CCM 2177) into crystalline structures has been reported in several studies. Hence, ions such as magnesium, barium, nickel and, most commonly, calcium (Ca²⁺) have proven to trigger both protein-protein and protein-substrate interactions involved in the two-stage non-classical pathway recrystallization followed by SbpA units. As a result, two dimensional, crystalline nanometric sheets in a highly ordered tetrameric state (p4) can be formed on top of different surfaces. The use of iron in its ferrous state (Fe²⁺) as self-assembly inducing candidate has been omitted so far due to its instability under aerobic conditions, tending to natural oxidation to the ferric (Fe³⁺) state. In this work, the potentiality of assembling fully functional S-layers from iron (II) salts (FeCl₂ and FeSO₄) is described for the first time. A combination of chemical (oxidation retardants) and electrical (−1 V potential) factors has been applied to effectively act against such an oxidizing trend. Formation of the respective crystalline films has been followed by means of Electrochemical Quartz Crystal Microbalance with Dissipation (EQCM-D) measurements and complementary Atomic Force Microscopy (AFM) topography studies, which prove the presence of squared lattice symmetry at the end of the recrystallization process. Both techniques, together with additional electrochemical tests performed over the ion permeability of both types of S-layer coatings formed, show the influence of the counterion chosen (chloride vs. sulphate) in the final packing and performance of the S-layer. The presence of an underlying Secondary Cell Wall Polymer (SCWP) as in the natural case contributes to pair both systems, due to the high lateral motility freedom provided by this biopolymer to SbpA units in comparison to uncoated substrates. Full article