The use of binary mixtures of 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide and aliphatic nitrile solvents as electrolyte for supercapacitors

Abstract The development of high voltage electrolytes is one of the key aspects for increasing both energy and power density of electrochemical double layer capacitors (EDLCs). The usage of blends of ionic liquids and organic solvents has been considered as a feasible strategy since these electrolytes combine high usable voltages and good transport properties at the same time. In this work, the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was mixed with two nitrile-based organic solvents, namely butyronitrile and adiponitrile, and the resulting blends were investigated regarding their usage in electrochemical double layer capacitors. Both blends have a high electrochemical stability, which was confirmed by prolonged float tests at 3.2 V, as well as, good transport properties. In fact, the butyronitrile blend reaches a conductivity of 17.14 mS·cm−1 and a viscosity of 2.46 mPa·s at 20 °C, which is better than the state-of-the-art electrolyte (1 mol·dm−3 of tetraethylammonium tetrafluoroborate in propylene carbonate).

Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors (Invited).

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface.In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time.In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1).Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.

New Method for the Estimation of Viscosity of Pure and Mixtures of Ionic Liquids Based on the UNIFAC–VISCO Model

A modified UNIFAC–VISCO group contribution method was developed for the correlation and prediction of viscosity of ionic liquids as a function of temperature at 0.1 MPa. In this original approach, cations and anions were regarded as peculiar molecular groups. The significance of this approach comes from the ability to calculate the viscosity of mixtures of ionic liquids as well as pure ionic liquids. Binary interaction parameters for selected cations and anions were determined by fitting the experimental viscosity data available in literature for selected ionic liquids. The temperature dependence on the viscosity of the cations and anions were fitted to a Vogel–Fulcher–Tamman behavior. Binary interaction parameters and VFT type fitting parameters were then used to determine the viscosity of pure and mixtures of ionic liquids with different combinations of cations and anions to ensure the validity of the prediction method. Consequently, the viscosities of binary ionic liquid mixtures were then calculated by using this prediction method. In this work, the viscosity data of pure ionic liquids and of binary mixtures of ionic liquids are successfully calculated from 293.15 K to 363.15 K at 0.1 MPa. All calculated viscosity data showed excellent agreement with experimental data with a relative absolute average deviation lower than 1.7%.

New Method Based on the UNIFAC–VISCO Model for the Estimation of Ionic Liquids Viscosity Using the Experimental Data Recommended by Mathematical Gnostics

The viscosity of ionic liquids (ILs) has been modeled as a function of temperature and at atmospheric pressure using a new method based on the UNIFAC–VISCO method. This model extends the calculations previously reported by our group (see Zhao et al. J. Chem. Eng. Data 2016, 61, 2160–2169) which used 154 experimental viscosity data points of 25 ionic liquids for regression of a set of binary interaction parameters and ion Vogel–Fulcher–Tammann (VFT) parameters. Discrepancies in the experimental data of the same IL affect the quality of the correlation and thus the development of the predictive method. In this work, mathematical gnostics was used to analyze the experimental data from different sources and recommend one set of reliable data for each IL. These recommended data (totally 819 data points) for 70 ILs were correlated using this model to obtain an extended set of binary interaction parameters and ion VFT parameters, with a regression accuracy of 1.4%. In addition, 966 experimental viscosity data points for 11 binary mixtures of ILs were collected from literature to establish this model. All the binary data consist of 128 training data points used for the optimization of binary interaction parameters and 838 test data points used for the comparison of the pure evaluated values. The relative average absolute deviation (RAAD) for training and test is 2.9% and 3.9%, respectively.

Carbon Dioxide Uptake from Natural Gas by Binary Ionic Liquid-Water mixtures

Carbon dioxide solubility in a set of carboxylate ionic liquids formulated with stoicheiometric amounts of water is found to be significantly higher than for other ionic liquids previously reported. This is due to synergistic chemical and physical absorption. The formulated ionic liquid/water mixtures show greatly enhanced carbon dioxide solubility relative to both anhydrous ionic liquids and aqueous ionic liquid solutions, and are competitive with commercial chemical absorbers, such as activated N-methyldiethanolamine or monoethanolamine.

The use of binary polymeric networks in stabilising polyethylene oxide solid dispersions

The objective of this study was to determine if a high Tg polymer (Eudragit® S100) could be used to stabilize amorphous domains of polyethylene oxide (PEO) and hence improve the stability of binary polymer systems containing celecoxib (CX). We propose a novel method of stabilizing the amorphous PEO solid dispersion through inclusion of a miscible, high Tg polymer, namely, that can form strong inter-polymer interactions. The effects of inter-polymer interactions and miscibility between PEO and Eudragit S100 are considered. Polymer blends were first manufactured via hot-melt extrusion at different PEO/S100 ratios (70/30, 50/50, and 30/70 wt/wt). Differential scanning calorimetry and dynamic mechanical thermal analysis data suggested a good miscibility between PEO and S100 polymer blends, particularly at the 50/50 ratio. To further evaluate the system, CX/PEO/S100 ternary mixtures were extruded. Immediately after hot-melt extrusion, a single Tg that increased with increasing S100 content (anti-plasticization) was observed in all ternary systems. The absence of powder X-ray diffractometry crystalline Bragg’s peaks also suggested amorphization of CX. Upon storage (40°C/75% relative humidity), the formulation containing PEO/S100 at a ratio of 50:50 was shown to be most stable. Fourier transform infrared studies confirmed the presence of hydrogen bonding between Eudragit S100 and PEO suggesting this was the principle reason for stabilization of the amorphous CX/PEO solid dispersion system.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

The crowded magnetosphere of the post-common-envelope binary QS Virginis

We present high-speed photometry and high-resolution spectroscopy of the eclipsing post-common-envelope binary QS Virginis (QS Vir). Our Ultraviolet and Visual Echelle Spectrograph (UVES) spectra span multiple orbits over more than a year and reveal the presence of several large prominences passing in front of both the M star and its white dwarf companion, allowing us to triangulate their positions. Despite showing small variations on a time-scale of days, they persist for more than a year and may last decades. One large prominence extends almost three stellar radii from the M star. Roche tomography reveals that the M star is heavily spotted and that these spots are long-lived and in relatively fixed locations, preferentially found on the hemisphere facing the white dwarf. We also determine precise binary and physical parameters for the system. We find that the 14 220 ± 350 K white dwarf is relatively massive, 0.782 ± 0.013 M⊙, and has a radius of 0.010 68 ± 0.000 07 R⊙, consistent with evolutionary models. The tidally distorted M star has a mass of 0.382 ± 0.006 M⊙ and a radius of 0.381 ± 0.003 R⊙, also consistent with evolutionary models. We find that the magnesium absorption line from the white dwarf is broader than expected. This could be due to rotation (implying a spin period of only ˜700 s), or due to a weak (˜100 kG) magnetic field, we favour the latter interpretation. Since the M star's radius is still within its Roche lobe and there is no evidence that it is overinflated, we conclude that QS Vir is most likely a pre-cataclysmic binary just about to become semidetached.

Rotational velocities of single and binary O-type stars in the Tarantula Nebula

Rotation is a key parameter in the evolution of massive stars, affecting their evolution, chemical yields, ionizing photon budget, and final fate. We determined the projected rotational velocity, υ e sin i, of ~330 O-type objects, i.e. ~210 spectroscopic single stars and ~110 primaries in binary systems, in the Tarantula nebula or 30 Doradus (30 Dor) region. The observations were taken using VLT/FLAMES and constitute the largest homogeneous dataset of multi-epoch spectroscopy of O-type stars currently available. The most distinctive feature of the υ e sin i distributions of the presumed-single stars and primaries in 30 Dor is a low-velocity peak at around 100 km s^-1. Stellar winds are not expected to have spun-down the bulk of the stars significantly since their arrival on the main sequence and therefore the peak in the single star sample is likely to represent the outcome of the formation process. Whereas the spin distribution of presumed-single stars shows a well developed tail of stars rotating more rapidly than 300 km s^-1, the sample of primaries does not feature such a high-velocity tail. The tail of the presumed-single star distribution is attributed for the most part - and could potentially be completely due - to spun-up binary products that appear as single stars or that have merged. This would be consistent with the lack of such post-interaction products in the binary sample, that is expected to be dominated by pre-interaction systems. The peak in this distribution is broader and is shifted toward somewhat higher spin rates compared to the distribution of presumed-single stars. Systems displaying large radial velocity variations, typical for short period systems, appear mostly responsible for these differences.

Design of binary polymeric systems containing ɩ-carrageenan and hydroxypropylcellulose for use in cataract surgery.

This study describes the design and characterisation of the rheological and mechanical properties of binary polymeric systems composed of 2-Hydroxypropylcellulose and ɩ-carrageenan, designed as ophthalmic viscoelastic devices (OVDs). Platforms were characterised using dilute solution, flow and oscillatory rheometry and texture profile analysis. Rheological synergy between the two polymers was observed both in the dilute and gel states. All platforms exhibited pseudoplastic flow. Increasing polymer concentrations significantly decreased the loss tangent and rate index yet increased the storage and loss moduli, consistency, gel hardness, compressibility and adhesiveness, the latter being related to the in-vivo retention properties of the platforms. Binary polymeric platforms exhibited unique physicochemical properties, properties that could not be engineered using mono-polymeric platforms. Using characterisation methods that provide information relevant to their clinical performance, low-cost binary platforms (3% hydroxypropylcellulose and either 1% or 2% ɩ-carrageenan) were identified that exhibited rheological, textural and viscoelastic properties advantageous for use as OVDs.

Bayesian Dependence Tests for Continuous, Binary and Mixed Continuous-Binary Variables

Tests for dependence of continuous, discrete and mixed continuous-discrete variables are ubiquitous in science. The goal of this paper is to derive Bayesian alternatives to frequentist null hypothesis significance tests for dependence. In particular, we will present three Bayesian tests for dependence of binary, continuous and mixed variables. These tests are nonparametric and based on the Dirichlet Process, which allows us to use the same prior model for all of them. Therefore, the tests are “consistent” among each other, in the sense that the probabilities that variables are dependent computed with these tests are commensurable across the different types of variables being tested. By means of simulations with artificial data, we show the effectiveness of the new tests.