Mixed Lithium and Sodium Ion Aprotic DMSO Electrolytes for Oxygen Reduction on Au and Pt Studied by DEMS and RRDE

In order to advance the development of metal-air batteries and solve possible problems, it is necessary to gain a fundamental understanding of the underlying reaction mechanisms. In this study we investigate the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER, from species formed during ORR) in Na+ containing dimethyl sulfoxide (DMSO) on poly and single crystalline Pt and Au electrodes. Using a rotating ring disk electrode (RRDE) generator collector setup and additional differential electrochemical mass spectrometry (DEMS), we investigate the ORR mechanism and product distribution. We found that the formation of adsorbed Na2O2, which inhibits further oxygen reduction, is kinetically favored on Pt overadsorption on Au. Peroxide formation occurs to a smaller extent on the single crystal electrodes of Pt than on the polycrystalline surface. Utilizing two different approaches, we were able to calculate the heterogeneous rate constants of the O2/O2− redox couple on Pt and Au and found a higher rate for Pt electrodes compared to Au. We will show that on both electrodes the first electron transfer (formation of superoxide) is the rate-determining step in the reaction mechanism. Small amounts of added Li+ in the electrolyte reduce the reversibility of the O2/O2− redox couples due to faster and more efficient blocking of the electrode by peroxide. Another effect is the positive potential shift of the peroxide formation on both electrodes. The reaction rate of the peroxide formation on the Au electrode increases when increasing the Li+ content in the electrolyte, whereas it remains unaffected on the Pt electrode. However, we can show that the mixed electrolytes promote the activity of peroxide oxidation on the Pt electrode compared to a pure Li+ electrolyte. Overall, we found that the addition of Li+ leads to a Li+-dominated mechanism (ORR onset and product distribution) as soon as the Li+ concentration exceeds the oxygen concentration. Graphical abstract

Size and charge correlations in spherical electric double layers: a case study with fully asymmetric mixed electrolytes within the solvent primitive model

Size and charge correlations in spherical electric double layers are investigated through Monte Carlo simulations and density functional theory, through a solvent primitive model representation.

Recent Advances in Scale Prediction: Approach and Limitations

Summary Numerous saturation indices and computer algorithms have been developed to determine whether, when, and where scale will form. However, scale prediction can still be challenging because the predictions from different models often differ significantly at extreme conditions. Furthermore, there is a great need to accurately interpret the partitioning of water (H2O), carbon dioxide (CO2), and hydrogen sulfide (H2S) between different phases, as well as the speciations of CO2 and H2S. This paper summarizes current developments in the equation-of-state (EOS) and Pitzer models to accurately model the partitioning of H2O, CO2, and H2S in hydrocarbon/aqueous phases and the aqueous ion activities at ultrahigh-temperature, ultrahigh-pressure, and mixed-electrolytes conditions. The equations derived from the Pitzer ion-interaction theory have been parameterized by regression of more than 10,000 experimental data from publications over the last 170-plus years using a genetic algorithm on the supercomputer DAVinCI at Rice University. With this new model, the 95% confidence intervals of the estimation errors for solution density are within 4×10–4 g/cm3. The solubility predictions of CO2 and H2S are accurate to within 4%. The saturation-index (SI) mean values for calcite (CaCO3), barite (BaSO4), gypsum (CaSO4·2H2O), anhydrite (CaSO4), and celestite (SrSO4) are accurate to within ±0.1—and for halite the values are within ±0.01—most of which are within experimental uncertainties. This model accurately defines the pH value of the production tubing at various temperature and pressure regimes and the risk of H2S exposure and corrosion. Furthermore, our model is able to predict the density of soluble chloride and sulfate (SO42−) salt solutions within ± 0.1% relative error. The ability to accurately predict the density of a given solution at temperature and pressure allows one to deduce when freshwater breakthrough will occur. In addition, accurate predictions can only be reliable with accurate data input. The need to improve the accuracy of scale prediction with quality data will also be discussed.

Physical and electrochemical properties of mixed electrolyte 1-ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide and ethylene carbonate as electrolytes for Li-ion batteries

Introduction: Ionic liquids (ILs) have become a prospective candidate to replace the conventional electrolytes based on the volatile organic-solvents in lithium-ion batteries. However, the drawbacks of high viscosity and low ionic conductivity have restricted the high rate capacity and energy density in practical batteries. With the aims to resolve these problems and design a safe electrolytes with high electrochemical stability, mixtures of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMITFSI) with different amounts of ethylene carbonate (EC) was prepared and characterized as electrolytes for Li-ion batteries. Methods: In this work, we investigated four factors to demonstrate the performance of EMITFSI as electrolytes for Li-ion batteries. These factors include: thermal properties of mixed electrolytes (Mettler Toledo DSC1 Star -DSC, Q500-TGA), Conductivity (HP- AC impedance spectroscopy), Viscosity (Ostwald viscometer CANNON) and electrochemical window (cyclic voltammetry-MGP2 Biologic Instrument). All experiments were repeated three times with the exception of TGA-DSC methods. Results: The study indicated that 20 % wt. ethylene carbonate (EC) when mixed with EMITFSI could significantly decrease the electrolyte viscosity while improving ionic conductivity and maintain similar electrochemical stability as pure ionic liquid. Lithium diffusion coefficient of mixed electrolytes was lower than commercial electrolytes based on conventional solvents, however, the thermal stability was enhanced. Conclusion: EMITFSI can be used to replace conventional carbonate-based liquids as a high-performance electrolyte for Li-ion batteries.