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The solubility of long-chain lithium polysulfides (nominally Li2S8) in sulfolane and sulfolane solutions of lithium perchlorate has been studied. It was found that the solubility of sulfur in the species of lithium octasulfide is significantly, by one to two orders of magnitude, higher than the solubility of elemental sulfur. The rate of Li2S8 formation and its solubility decreases, as the concentration of LiClO4 increases. The absorption spectra of Li2S8 are similar to the absorption spectra of elemental sulfur except for the position of the long-wavelength absorption bands, which have a significant bathochromic shift. [ABSTRACT FROM AUTHOR]

Chemical absorption is currently the most mature carbon capture technology, but it has high energy consumption. Phase change absorbents have great potential for reducing energy consumption. In this paper, an attempt is made to combine the commonly used organic phase splitter and physical phase splitter to explore the comprehensive performance of the absorber under the joint action of the two. Hydroxyethyl ethylenediamine (AEEA) was used as the active amine, N,N‐diethylethanolamine (DEEA) as the organic phase splitter, and sulfolane as the physical phase splitter. Different molar ratios of the three reagents were carried out to screen out the combinations with superior split‐phase effects, and the absorption and desorption characteristics of the combination of AEEA/DEEA/sulfolane were investigated in terms of absorption performance, desorption performance, cycling performance, and physical parameters. The results showed that the combination of 2 M AEEA/1 M DEEA/4 M sulfolane was the most advantageous, with an absorption load up to 2.17 mol/L, a volume of the rich phase accounting for about 64%, an initial absorption rate up to 0.1756 mol · L−1 · min−1, a desorption rate of 75.5% at the desorption temperature of 393.15 K, and the rich‐phase viscosity had a great advantage over the other molar ratio combinations. The changes of the components before and after phase separation were analyzed by 13C NMR to investigate the phase separation mechanism, and the five repeated cycle tests showed that the absorption load was stable, the desorption capacity was strong, and the phase separation performance was good. [ABSTRACT FROM AUTHOR]

To increase the accuracy of determining the lithium cation transference numbers we proposed to measure them at different values of the polarizing voltage and extrapolate the calculated values to the zero value of the polarizing voltage. It was established that the lithium cation transference numbers increased linearly with the increasing concentration of LiClO4 solutions in sulfolane. It is assumed that the increase in the lithium cation transference numbers takes place due to the change in lithium perchlorate state in sulfolane solution and the mechanism of ion transfer. It was shown that the maximum cation conductivity was achieved at the concentration of lithium perchlorate sulfolane solution of about 2M.

The effect of lithium polysulfides on the amount and ratio of electrochemically active metallic lithium, electrochemically inactive metallic lithium, and chemically formed lithium compounds in the cathodic deposits formed on a stainless-steel electrode during galvanostatic cycling in 1 М LiClO4 solution in sulfolane at 15, 30, 45, and 60°C is studied using the method we have developed earlier. It is shown that the increase in temperature leads to increase in the Coulomb efficiency of cycling and the amount of electrochemically active metallic lithium; a decrease in the amount of electrochemically inactive metallic lithium, regardless of the presence of lithium polysulfides in the electrolyte. When lithium polysulfides have been introduced into the electrolyte, an increase in the Coulomb efficiency of the metallic lithium cycling and a change in the ratio of various forms of lithium in the cathodic deposits toward an increase in electrochemically active lithium by about 1.5 times are observed. The lithium polysulfides are assumed to contribute to the dissolution of electrochemically inactive metallic lithium, forming an interfacial "sulfide" film at the electrode, which possessed high ionic conductivity and good protective properties, the more so, at elevated temperatures. [ABSTRACT FROM AUTHOR]

A study is performed of the physicochemical properties (ionic conductivity, viscosity, and density in the 30–50°C range of temperatures) and the electrochemical and thermal stability of lithium bis(trifluoromethanesulfonyl)imide solutions in sulfolane in the 0.001–1.89 M range of concentrations. It is shown that lithium bis(trifluoromethanesulfonyl)imide solutions in sulfolane exhibit high electrochemical stability (5.75 V vs. Li/Li+) and moderate ionic conductivity (2.75 × 10−3 Ω−1 cm−1 at 30°C for a 1 M solution), which are comparable to the respective parameters of sulfolane solutions of lithium hexafluorophosphate. The structure and transport properties of sulfolane solutions of lithium bis(trifluoromethanesulfonyl)imide are determined by their concentrations. In dilute solutions, lithium bis(trifluoromethanesulfonyl)imide is weakly associated. The degree of electrolytic dissociation of LiN(SO2CF3)2 initially falls and then rises upon an increase in its concentration. The electrolytic dissociation of lithium bis(trifluoromethanesulfonyl)imide rises along with its concentration, due to the formation of ion triplets and more complex ion associates. The constant of association and limit equivalent conductivity of LiN(SO2CF3)2 in sulfolane rise along with temperature, due to a drop in the degree of self-association and the degradation of the solvent's structure. A specific feature of sulfolane solutions of lithium bis(trifluoromethanesulfonyl)imide is their tendency to form stable supercooled solutions. [ABSTRACT FROM AUTHOR]

The temperature dependencies of physical and chemical properties (viscosity, density, electrical conductivity) and the melting temperature of 1M solutions of lithium salts (LiClO4 and LiBF4) in the mixture of sulfolane and sulfurous anhydride (∼1M) were studied. It was shown that the introduction of 1M (5% wt.) of sulfurous anhydride into 1M solutions of LiClO4 and LiBF4 in sulfolane increased the specific and corrected electrical conductivity, densities, activation energy of electrical conductivity and viscous flow of electrolyte solutions; and reduced viscosity and melting temperatures.

Sulfolane is an emerging contaminant, miscible in pure water. The correlation between mixing behavior and transport of sulfolane with sulfate and chloride salts is not fully understood. Sulfate salts (e.g., Na2SO4) decrease the solubility of sulfolane in water. Specifically, solutions with 30wt% sulfolane separated into bulk phases with 130 g/kg Na2SO4 (2.4 mol% Na2SO4 relative to the total mixture) and emulsions formed with lower concentrations of Na2SO4 (41 g/kg or 0.7 mol% Na2SO4 relative to the total mixture). This is not observed with chlorides at these same concentrations. Na2SO4 enhanced sulfolane sorption onto montmorillonite clay, with 0.2 g sulfolane sorbed/g clay at high Na2SO4 concentrations (40.7 g Na2SO4/kg solution). As a result, Na2SO4 delayed sulfolane migration in model clayey fractures, compared to pure water. Sulfolane and co-contaminants such as toluene reciprocally influence their miscibility in water. Sulfolane emulsified toluene in pure water, while Na2SO4 supressed emulsification. In turn, sulfolane partitioned in toluene, and Na2SO4 enhanced this behavior by decreasing sulfolane miscibility in water. In flow tests conducted with 0.7 mol% Na2SO4 and 30wt% sulfolane (relative to water), the sulfolane concentration at the outlet is lower than that at the inlet for up to 80% of the total eluted volume. Therefore, in model sandy aquifers, the vertical migration of sulfolane was delayed with Na2SO4 and toluene, which floated on water and was trapped in soil pores due to capillary forces. Chloride salts had a less significant effect on toluene solubility in water and on its migration through model porous media. [ABSTRACT FROM AUTHOR]

Naphtha cracking processes call for low aromatic feedstocks to satisfy the operational considerations regarding the quality of their feedstocks. Therefore, the issue of the aromatics removal from petroleum fractions has become more serious. In this study, the experimental investigation and thermodynamic modeling of the liquid-liquid equilibria of the quinary system naphtha cut (including paraffinic, naphthenic, and aromatic species), sulfolane, and water, over the temperature range of 303.2 to 333.2 K, have been studied. The molecular representatives of paraffinic, naphthenic, and aromatic species of naphtha cut have been determined based on different objective functions. Physical properties estimation and modeling of equilibrium data reveal higher accuracy of vapor pressure- and viscosity-based objective functions in the structural modeling of naphtha cut. The rootmean-square deviations for the mentioned functions were determined to be about 1.47 and 1.48%, respectively. Thermodynamic modeling with the predictive UNIFAC model showed a good agreement with the experimental measurements. Also, the interaction coefficients extracted from the 75 ºC equilibrium data led to minimum deviation in the equilibrium modeling. Finally, the phase diagrams show the noticeable effect of water content and the small effect of temperature on the system equilibria. [ABSTRACT FROM AUTHOR]

A simple method for the synthesis of five- and six-membered ring sulfone carbamates was elaborated. The method includes reaction of the corresponding starting alcohols with trichloroacetyl isocyanate following the hydrolysis of trichloroacetyl protecting group with potassium carbonate in methanol. Rh2(OAc)4 catalyzed cyclization of carbamates was investigated. It was shown that carbamates with saturated sulfone moiety tend to give products of elimination of carbamic acid (corresponding unsaturated sulfones) due to high acidity of C–H bond in α-position of sulfone ring. Unsaturated sulfone carbamate (1,1-dioxido-2,3-dihydrothiophen-3-yl carbamate) in similar reaction conditions afforded new heterocyclic system confirmed by 2D NMR: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3-one 2,2-dioxide. This result can be explained by more favorable aziridination of the double C=C bond by the nitrenoid intermediate compared to the elimination pathway. In silico pharmacological profile of new heterocyclic compound was evaluated. The compound showed good ADME and acute toxicity properties and high probability level of anticancer activity for prostate carcinoma cell line PC-3. [ABSTRACT FROM AUTHOR]

The physicochemical properties and the phase state of sulfolane (1)—ethyl isobutyl sulfone (2) mixtures and 1 M LiClO4 solutions based on these mixtures were studied in the temperature range from 50 to −70 °C. The mixtures form an eutectic with a temperature of −31.2 °C. The phase diagram of the binary system 1–2 exhibits two solidus lines owing to the ability of sulfolane to exist in three phase states (crystalline, mesomorphic, and liquid). Solutions of LiClO4 in the mixtures of sulfones 1 and 2 containing more than 15 mol.% of 2 are in the liquid state down to −70 °C. The specific conductivity and viscosity isotherms of the 1 M LiClO4 solutions in the mixtures of sulfones 1 and 2, depending on the composition of the electrolyte solvent, are nonlinear, namely, specific conductivity is lower while the viscosity is higher than the corresponding additive values. The maximum degree of electrolytic dissociation of LiClO4 is achieved in the sulfone mixtures containing about 15% mol. of sulfone 2. Electrolyte solutions based on the mixtures of sulfones 1 and 2 containing more than 15 mol.% of 2 can be used as electrolytes for low-temperature lithium-ion and post-lithium-ion batteries. [ABSTRACT FROM AUTHOR]

An approach for the determination of the melting point of electrolyte solutions using the molecular dynamics method is considered. In order to calculate the melting point of the electrolyte solutions, it is proposed to successively calculate the density of the system using the molecular dynamics approach in the temperature range, which includes the expected melting point. The melting point was identified as the temperature at which the temperature dependence of density of the studied solutions registered an inflection point. The proposed approach is verified using sulfolane and solutions of lithium salts in sulfolane as examples, and a good agreement between the melting point determined using differential scanning calorimetry and the calculated temperature is observed. The discrepancy between the calculated and the experimental values of the densities of the studied systems did not exceed 3%. [ABSTRACT FROM AUTHOR]

Due to the unsatisfactory electrode/electrolyte interface, the metallic Zn dendrites and corrosion are easily induced, severely hindering the applications of zinc-ion batteries (ZIBs). Herein, a strategy that engineers the interfacial double layer by an extremely low concentration of sulfolane is proposed to tune the Zn stripping/plating behavior. It is revealed that the highly-polar sulfolane can predominately occupy the inner Helmholtz layer over water, and then regulate the upcoming Zn2+ to directly deposit downward. Simultaneously, the widened Helmholtz layer can weaken the electric field intensity, which will generate more nucleation sites and reduce the nuclei radius, thereby promoting uniform zinc deposition as well. Moreover, corrosion byproducts can be inhibited since fewer water molecules can contact the Zn electrodes. Consequently, the battery performance can be naturally optimized. With an optimum amount of sulfolane, the Zn∥Zn battery can operate for more than 1,100 h under 1 mA cm−2 and 1 mAh cm−2. And the as-constructed Zn∥NaV3O8·1.5H2O battery demonstrates considerably higher cycling stability than that without sulfolane. Overall, this work has provided a deep insight into constructing a functional interfacial double layer to regulate zinc deposition, which can also act as a reference for other metal-based batteries. [ABSTRACT FROM AUTHOR]

Abstract Sulfolane is extensively used as an extractive solvent in sour-gas processing plants in the petrochemical industry. After repeated use, deteriorated sulfolane becomes corrosive and may leak into the environment to threaten aquatic and terrestrial organisms or cause shock loading of wastewater treatment systems. It is therefore important to remove sulfolane from the environment and maintain stable wastewater treatment efficiency. To address this issue, bioaugmentation provides a solution by adding specific microorganisms into the biological treatment system to speed up the contaminant degradation rate. Isolation of microbes capable of degrading target contaminant is key point. Understanding the physiological characteristics of isolated microbes is indispensable for subsequent successful applications. In this study, sulfolane degrading bacteria from the activated sludge of a petrochemical plant were enriched using 200–1000 mg L−1 sulfolane and then isolated. After confirming their sulfolane degrading ability, sulfolane biodegradation was then investigated under various pHs, sulfolane and sulfate concentrations. Enrichment could enhance the sulfolane degrading rate of the mixed culture from 3.9 to 7.1 times. Three strains (strain Y-a, Y-d and Y-f) capable of degrading sulfolane were isolated. The degrading microbes were identified as Cupriavidus sp. using 16S rDNA sequencing. Sulfolane concentration biodegraded by strain Cupriavidus sp. Y-d at pH of 7–9 was 1.40–1.45 times higher than that at pH of 6. The optimal pH for strain Cupriavidus sp. Y-d to degrade sulfolane was 8. When increasing the sulfolane concentration from 500 to 2000 mg L−1, the specific growth rate and specific substrate utilization rate increased from 0.19 to 0.48 d−1 and 0.48 to 0.59 d−1, respectively. Strain Cupriavidus sp. Y-d was capable of degrading 2000 mg L−1 sulfolane. Sulfate concentrations higher than 2511 mg L−1 had a negative effect on sulfolane biodegradation.

In this work, 193 nm ultraviolet photodissociation-mass spectrometry (UVPD-MS) was applied to investigate supercharging reagent sulfolane in protein sequence and structure characterization. All datasets were collected by using an Orbitrap MS system equipped with an ArF 193 nm EX50 excimer Laser. The 193 nm UV laser has the advantages of high brightness, good stability, and propagate in air, which can directly excite and dissociate the protein backbone within 5 ns (single pulse). Previous reports demonstrated that the partial protein high-order structures and non-covalent interactions could be retained in the UVPD fragments and the site-specific fragmentation yields (FYs) revealed the dynamic protein structure alterations under different conditions. Therefore, the combination of UVPD with nMS provides a new research paradigm for the characterization of protein structure changes. In this work, we further demonstrated 193 nm UVPD was superior to high-energy collision induced dissociation (HCD) in fragmenting and sequencing the non-denatured carbonic anhydrase II (CA) generated in native electrospray ionization (ESI). UVPD could efficiently activate and fragmentate the non-denatured CA with different charge states in just 5 ns, achieving cleavage sequence coverage 79.8% for CA Z10. Then, 0.25% supercharging reagent sulfolane was added into the protein solution and the CA charge distribution was significantly moved to higher charge states under identical native ESI conditions. However, higher-order structures (HOS) and non-covalent interactions could be obtained as the CA charge distribution was still concentrated and significantly different from the spectra features of denatured CA. The UVPD cleavage sequence coverage of the CA was increased to 87.2%, including the regions that were difficult to be dissociated and characterized without sulfolane addition. In addition, the non-covalent of CA and Zn2+ remained stable, indicating that the addition of sulfoxide had little influence on the Zn2+ binding region. The UVPD sequence coverage of CA Z11 was increased by 7.4% after the addition of sulfoxide, but the site FYs were almost not changed, demonstrating the corresponding local structures were nearly not changed. However, the higher charge states introduced by sulfolane also exhibited the risk of inducing specific structure alteration of part of protein regions. In conclusion, it was infered that supercharging reagent is efficient in modulating the charge state distribution of proteins in native ESI-MS characterization and can expand the MS detection mass range. The introduction of supercharging reagent can further improve the UVPD sequence coverage, including the structure-compact regions hard to be fragmented. Although part of the protein HOS and non-covalent interactions seems retained, the influence of higher charge states on protein structures should be considered in dynamic protein structure investigation.

The solubility of sulfur in sulfolane and solutions of lithium salts [LiBF4, LiClO4, LiPF6, LiSO3CF3 and LiN(SO2CF3)2] in sulfolane, which are promising electrolytes for lithium-sulfur batteries, was determined by UV-vis spectroscopy. It was found that the solubility of sulfur in sulfolane at 30°C is 82.0 mM, and in sulfolane solutions of lithium salts (1 M) it is 4–9 times lower. The dependence of sulfur solubility on the concentration of lithium salts is not linear: it is 32.9 and 5.8 mM for sulfolane solutions containing 0.5 and 2.35 M of LiClO4, respectively. [ABSTRACT FROM AUTHOR]

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An ethylene carbonate‐free electrolyte composed of 1 M lithium bis(fluorosulfonyl) imide (LiFSI) in sulfolane (SL) is studied here for LiNi0.5Mn1.5O4‐graphite full‐cells. An important focus on the evaluation of the anodic stability of the SL electrolyte and the passivation layers formed on LiNi0.5Mn1.5O4 (LNMO) and graphite is being analysed along with intermittent current interruption (ICI) technique to observe the resistance while cycling. The results show that the sulfolane electrolyte shows more degradation at higher potentials unlike previous reports which suggested higher oxidative stability. However, the passivation layers formed due to this electrolyte degradation prevents further degradation. The resistance measurements show that major resistance arises from the cathode. The pressure evolution during the formation cycles suggests that there is lower gas evolution with sulfolane electrolyte than in the conventional electrolyte. The study opens a new outlook on the sulfolane based electrolyte especially on its oxidative/anodic stability. [ABSTRACT FROM AUTHOR]

Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, H3PO4-modified H-ZSM-5, H3PW12O40·14H2O and Cs2.5H0.5PW12O40, in the presence of sulfolane ((CH2)4SO2) as a dispersing agent under atmospheric pressure N2 in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke. [ABSTRACT FROM AUTHOR]

Some previous studies have found the synergistic effect of mixed anions in dual‐ion batteries (DIBs). In this work, both lithium tetrafluoroborate (LiBF4) and lithium difluoro(oxalato)borate (LiDFOB) were dissolved in sulfolane (SL) solvent, and the resultant solutions were applied for DIBs. The storage behavior of mixed anions in natural graphite positive electrodes was investigated. In‐situ X‐ray diffraction measurements revealed both anions could participate in the formation of graphite intercalation compounds. Their evolution followed with the decreasing tendency of discharge capacities as the content of LiDFOB increased in solutions. The exchange of anions was discussed. [ABSTRACT FROM AUTHOR]

Sulfolane is extensively used as an extractive solvent in sour-gas processing plants in the petrochemical industry. After repeated use, deteriorated sulfolane becomes corrosive and may leak into the environment to threaten aquatic and terrestrial organisms or cause shock loading of wastewater treatment systems. It is therefore important to remove sulfolane from the environment and maintain stable wastewater treatment efficiency. To address this issue, bioaugmentation provides a solution by adding specific microorganisms into the biological treatment system to speed up the contaminant degradation rate. Isolation of microbes capable of degrading target contaminant is key point. Understanding the physiological characteristics of isolated microbes is indispensable for subsequent successful applications. In this study, sulfolane degrading bacteria from the activated sludge of a petrochemical plant were enriched using 200–1000 mg L−1 sulfolane and then isolated. After confirming their sulfolane degrading ability, sulfolane biodegradation was then investigated under various pHs, sulfolane and sulfate concentrations. Enrichment could enhance the sulfolane degrading rate of the mixed culture from 3.9 to 7.1 times. Three strains (strain Y-a, Y-d and Y-f) capable of degrading sulfolane were isolated. The degrading microbes were identified as Cupriavidus sp. using 16S rDNA sequencing. Sulfolane concentration biodegraded by strain Cupriavidus sp. Y-d at pH of 7–9 was 1.40–1.45 times higher than that at pH of 6. The optimal pH for strain Cupriavidus sp. Y-d to degrade sulfolane was 8. When increasing the sulfolane concentration from 500 to 2000 mg L−1, the specific growth rate and specific substrate utilization rate increased from 0.19 to 0.48 d−1 and 0.48 to 0.59 d−1, respectively. Strain Cupriavidus sp. Y-d was capable of degrading 2000 mg L−1 sulfolane. Sulfate concentrations higher than 2511 mg L−1 had a negative effect on sulfolane biodegradation. [ABSTRACT FROM AUTHOR]

Organic electrolytes based on different solvents (propylene carbonate, γ-butyrolactone, sulfolane, and benzonitrile) with high boiling points have been studied in supercapacitors. The cyclic voltammetry data, dependence of capacitance, internal resistance on voltage, and endurance tests indicate that a solution of spiro-(1,1′)-bipyrrolidinium tetrafluoroborate (SBP-BF4) in benzonitrile is one of the most reliable electrolytes in a voltage range of about 2.5 V up to temperature of 100-110°C . The high electrochemical stability of benzonitrile under such harsh conditions can be explained by the absence of an SEI film formation process on the electrode surface that doesn’t cause a noticeable internal resistance increase and capacity decrease when voltage is increased. [ABSTRACT FROM AUTHOR]

The structure of lithium polysulfides has been studied using density functional theory. The thermodynamic characteristics of their most probable transformations in sulfolane (Sl) have been evaluated. Various models of lithium oxidation and reduction of sulfur are studied by the PBE1PBE/6–311 + G(d,p) approximation, considering the influence of the solvation environment by the IEF‐PCM. The most probable mechanism of sulfur reduction in the Li–S system is considered (Voltage vs. Li/Li+): (I) S8 + 2Li → Li2S8 (2.6 V), (II) Li2S8 + 2Li → 2Li2S4 (2.3 V), (III) Li2S4 + 2Li → 2Li2S2 (1.6 V), (IV) Li2S2 + 2Li → 2Li2S (1.3 V). It was shown that the potential of the reduction of sulfur compounds is substantially determined by the composition of the solvate complexes of lithium polysulfides. The solvate complex Li2S8·2Sl is the most stable in the form of a «broken crown». The preference of the fragmentation of Li2S8 into LiS4− and LiS4 upon electron transfer is shown using FMO theory. [ABSTRACT FROM AUTHOR]

In this work, 193 nm ultraviolet photodissociation-mass spectrometry (UVPD-MS) was applied to investigate supercharging reagent sulfolane in protein sequence and structure characterization. All datasets were collected by using an Orbitrap MS system equipped with an ArF 193 nm EX50 excimer Laser. The 193 nm UV laser has the advantages of high brightness, good stability, and propagate in air, which can directly excite and dissociate the protein backbone within 5 ns (single pulse). Previous reports demonstrated that the partial protein high-order structures and non-covalent interactions could be retained in the UVPD fragments and the site-specific fragmentation yields (FYs) revealed the dynamic protein structure alterations under different conditions. Therefore, the combination of UVPD with nMS provides a new research paradigm for the characterization of protein structure changes. In this work, we further demonstrated 193 nm UVPD was superior to high-energy collision induced dissociation (HCD) in fragmenting and sequencing the non-denatured carbonic anhydrase II (CA) generated in native electrospray ionization (ESI). UVPD could efficiently activate and fragmentate the non-denatured CA with different charge states in just 5 ns, achieving cleavage sequence coverage 79.8% for CA Z10. Then, 0.25% supercharging reagent sulfolane was added into the protein solution and the CA charge distribution was significantly moved to higher charge states under identical native ESI conditions. However, higher-order structures (HOS) and non-covalent interactions could be obtained as the CA charge distribution was still concentrated and significantly different from the spectra features of denatured CA. The UVPD cleavage sequence coverage of the CA was increased to 87.2%, including the regions that were difficult to be dissociated and characterized without sulfolane addition. In addition, the non-covalent of CA and Zn2+ remained stable, indicating that the addition of sulfoxide had little influence on the Zn2+ binding region. The UVPD sequence coverage of CA Z11 was increased by 7.4% after the addition of sulfoxide, but the site FYs were almost not changed, demonstrating the corresponding local structures were nearly not changed. However, the higher charge states introduced by sulfolane also exhibited the risk of inducing specific structure alteration of part of protein regions. In conclusion, it was infered that supercharging reagent is efficient in modulating the charge state distribution of proteins in native ESI-MS characterization and can expand the MS detection mass range. The introduction of supercharging reagent can further improve the UVPD sequence coverage, including the structure-compact regions hard to be fragmented. Although part of the protein HOS and non-covalent interactions seems retained, the influence of higher charge states on protein structures should be considered in dynamic protein structure investigation. [ABSTRACT FROM AUTHOR]

A simple and convenient method has been developed for the quantitative determination of various forms of lithium in cathodic deposits formed on a stainless steel electrode during cycling, based on measuring the amount of hydrogen released during their interaction with protic solvents. The amount and ratio of electrochemically active metallic lithium, electrochemically inactive metallic lithium, and chemically bound lithium in the composition of cathode deposits formed on a steel electrode during galvanostatic cycling in sulfolane and propylene carbonate solutions of LiClO4 were determined. A method is proposed for determining the amount of an electrolyte solvent chemically reacted with metallic lithium. It has been found that, regardless of the solvent nature, the molar ratio of the reacted solvent to freshly formed lithium lies in the range of 0.84–0.85. It is assumed that the interaction of freshly formed metallic lithium with an electrolyte solvent occurs in a molar ratio of 1 : 1. The underestimated value of the reacted solvent–freshly formed lithium ratio is explained by the interaction of freshly precipitated lithium with a salt anion, which results in the formation of lithium oxide. It has been shown that the rate of destruction of sulfolane during cycling of the lithium electrode is approximately 1.5 times higher than the rate of destruction of propylene carbonate. Propylene carbonate, when interacting with freshly formed metallic lithium, forms surface films with better protective properties than sulfolane, which leads to a decrease in the rate of its interaction with metallic lithium and an increase in the Coulomb efficiency and the duration of the lithium electrode cycling. [ABSTRACT FROM AUTHOR]

Sodium metal anodes have attracted great attention for the development of a next generation of high-energy batteries because of their high theoretical capacity (1166 mAh·g−1), low redox potential (−2.71 V vs. SHE), and abundance. However, sodium reacts with most of the liquid electrolytes described to date and it has the shortcoming of dendrite formation during sodium deposition. Several strategies have been proposed to overcome these issues, including the incorporation of electrolyte additives. This work reports on the use of SO2 and sulfolane as additives in organic electrolytes to modify the sodium–electrolyte interphase, making the sodium plating/stripping process more robust. Not only is the process more stable in the case of sodium metal anodes, but also the use of copper substrates is enabled. In fact, high-quality sodium films on copper have been attained by adding small mole fractions of the additives, which paves the way for the development of anode-free batteries. In a general vein, this work stresses the importance of researching on compatible and cost-effective additives that can be easily implemented in practice. [ABSTRACT FROM AUTHOR]

High-voltage Li metal battery (HV-LMB) is one of the most promising energy storage technologies to achieve ultrahigh energy density. Nevertheless, electrolytes reported to date are difficult to simultaneously stabilize the Li metal anode and high-voltage cathode, especially without the assistance of expensive and corrosive high-concentration Li salts. Herein, a dual-interphase-stabilizing (DIS) and safe electrolyte that bypasses the high-concentration Li salt is reported. The electrolyte consists of high-flash-point sulfolane as solvent, molecular-orbital-engineered additives that enable stable B-F rich cathodic interphase, and unique C-F rich organic anodic interphase. The stable cycling of both Li metal anode and 4.75 V-LiCoO 2 cathode in the DIS electrolyte (> 500 cycles) is demonstrated. HV-LMB pouch cells of a high energy density (435 Wh kg -1 ) can sustainably operate for more than 100 cycles. Moreover, the low cost and high thermal stability of the DIS electrolyte offer superior cost-effectiveness and safety for large-scale applications of HV-LMBs in the future., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

For lithium-sulfur (Li-S) batteries, high-concentration electrolyte that inhibits the dissolution of Li polysulfide has been widely studied; one such electrolyte contains sulfolane. This study investigates the conditions under which a microporous activated carbon cathode, derived from azurmic acid, operates stably in a sulfolane-based electrolyte. We expected this cathode to maintain a stable capacity in a sulfolane-based electrolyte because its micropores stabilize the S species. However, Li-S batteries containing this cathode and electrolyte exhibit significant capacity decay during cycling. The cutoff voltage during charge-discharge cycling is varied to suppress the capacity decay. At a discharge voltage of 1.4 V or lower, the cycle life of the Li-S batteries is significantly reduced. Conversely, increasing the cutoff voltage during discharge suppresses the capacity decay of Li-S batteries. On the other hand, increasing the upper voltage limit during charging increases the reversible capacity. Thus, the operating voltage range is optimized. This study indicates that the voltage range of Li-S batteries should be carefully determined depending on the type of cathode material and electrolyte.

The non‐flammability and high oxidation stability of sulfolane (SL) make it an excellent electrolyte candidate for lithium‐ion batteries (LIBs). However, its incompatibility with graphitic anode prevents the realization of these advantages. To understand how this incompatibility arises on molecular level so that it can be suppressed, we combined theoretical calculation and experimental characterization and reveal that the primary Li+ solvation sheath in SL is depleted of fluorine source. Upon reduction, SL in such fluorine‐poor solvation sheath generates insoluble dimer with poor electronic insulation, hence leading to slow but sustained parasitic reactions. When fluorine content in Li+‐SL solvation sheath is increased via salt concentration, a high stability LiF‐rich interphase on graphite can be formed. This new understanding of the failure mechanism of graphite in SL‐based electrolyte is of great significance in unlocking many possible electrolyte solvent candidates for the high‐voltage cathode materials for next‐generation LIBs. [ABSTRACT FROM AUTHOR]

For patients with myelofibrosis, allogeneic hematopoietic stem cell transplantation (allo-HSCT) remains the only curative treatment to date. Busulfan-based conditioning regimens are commonly used, although high inter-individual variability (IIV) in busulfan drug exposure makes individual dose selection challenging. Since data regarding the IIV in patients with myelofibrosis are sparse, this study aimed to develop a population pharmacokinetic (PopPK) model of busulfan and its metabolite sulfolane in patients with myelofibrosis. The influence of patient-specific covariates on the pharmacokinetics of drug and metabolite was assessed using non-linear mixed effects modeling in NONMEM®. We obtained 523 plasma concentrations of busulfan and its metabolite sulfolane from 37 patients with myelofibrosis. The final model showed a population clearance (CL) and volume of distribution (Vd) of 0.217 L/h/kg and 0.82 L/kg for busulfan and 0.021 L/h/kg and 0.65 L/kg for its metabolite. Total body weight (TBW) and a single-nucleotide polymorphism of glutathione-S-transferase A1 (GSTA1 SNP) displayed a significant impact on volume of distribution and metabolite clearance, respectively. This is the first PopPK-model developed to describe busulfan's pharmacokinetics in patients with myelofibrosis. Incorporating its metabolite sulfolane into the model not only allowed the characterization of the covariate relationship between GSTA1 and the clearance of the metabolite but also improved the understanding of busulfan's metabolic pathway. [ABSTRACT FROM AUTHOR]

Aqueous electrolytes show the potential of application for high‐performance supercapacitors. However, their limited operating voltages set limits for widespread applications. Herein, the feasibility of applying the sulfolane (SL)‐saturated 3 m LiTFSI aqueous electrolytes for supercapacitors is shown. These electrolytes possess high conductivities and wide electrochemical stable windows (ESWs), demonstrating the potential applications in high‐voltage supercapacitors. Activated carbon//3 m LiTFSI SL/Water //activated carbon supercapacitor is assembled to possess a high voltage of 2.5 V and outstanding capacitive performance (106 F g−1 at 0.5 A g−1, >10 000 cycles). Also, a high areal capacitance up to 1.52 F cm−2 is obtained by applying a high mass loading electrode (13.06 mg cm−2). Furthermore, a flexible symmetric semi‐solid‐state supercapacitor (2.5 V) is fabricated. Impressive performance can be obtained. Thus, the finding suggests a promising electrolyte design for high‐voltage aqueous supercapacitors. [ABSTRACT FROM AUTHOR]

A study is performed of the possibility of using gas–liquid chromatography (GLC) to determine the composition of solutions of lithium salts in aprotic dipolar solvents and solvate ionic liquids. The objects of study are solutions of lithium perchlorate and lithium trifluoromethanesulfonate in sulfolane and solvate complexes of lithium perchlorate with sulfolane obtained in two ways: direct interaction of the initial components in a given molar ratio and interaction of the components in a common solvent with its subsequent removal via evaporation. It is shown that GLC is a convenient way of determining the content of a solvating solvent in the composition of solutions and solvate ionic liquids. The presence of lithium salt in the analyzed solutions does not affect the period of retention; instead, it raises the degree of asymmetry of the chromatographic peak of the solvent and manifestation of the tailing effect. It is found that the presence of salt in the considered system also does not reduce the accuracy of determining the solvent content. The error in determining the content of solvent in solutions of lithium salts and solvate complexes by GLC is no greater than 1%. [ABSTRACT FROM AUTHOR]

Moving from organic to aqueous lithium-ion batteries (ALIBs) would be an interesting feat. As of today, we have water-in-salt electrolytes (WISEs) that were developed primarily to expand the electrochemical stability window of traditional aqueous electrolytes. However, their cathodic limits do not enable the use of high-capacity negative electrodes and the very high concentrations of expensive heavily fluorinated salts, often >20 mol kg−1, hinder any feasible implementation of LIBs based on WISEs. A hybrid organic/aqueous electrolyte based on LiFTFSI dissolved in sulfolane and water is here presented as an alternative, where sulfolane is used to tune and reduce the water activity, by altering the Li+ cation first solvation shell, and thereby the cathodic limit can be pushed to <1.0 V vs. Li+/Li even at a comparatively moderate salt concentration (7.8 mol kg−1). This enables long-term operation of an Li 4 Ti 5 O 12 ⎪hybrid electrolyte⎪LiMn 2 O 4 2.4 V cell with a specific energy of 156 Wh kg AM −1. • Three-component electrolytes with sulfolane, water and lithium salt were studied. • The highest concentrated electrolyte is coupled with LTO and LMO as the anode and the cathode. • The cell shows has excellent cycling stability and safety. • The interactions among the different components were studied by solvation models. [ABSTRACT FROM AUTHOR]

Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, H3PO4-modified H-ZSM-5, H3PW12O40·14H2O and Cs2.5H0.5PW12O40, in the presence of sulfolane ((CH2)4SO2) as a dispersing agent under atmospheric pressure N2 in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke.

Binder‐ and conducting additive‐free Si–O–C composite layers are deposited electrochemically under potentiostatic conditions from sulfolane‐based organic electrolyte. Quartz crystal microbalance with damping monitoring is used for evaluation of the layer growth and its physical properties. The sodiation–desodiation performance of the material is afterward explored in Na‐ion electrolyte. In terms of specific capacity, rate capability, and long‐term electrochemical stability, the experiments confirm the advantages of applying the electrochemically formed Si–O–C structure as anode for Na‐ion batteries. The material displays high (722 mAh g−1) initial reversible capacity at j = 70 mA g−1 and preserves stable long‐term capacity of 540 mAh g−1 for at least 400 galvanostatic cycles, measured at j = 150 mA g−1. The observed high performance can be attributed to its improved mechanical stability and accelerated Na‐ion transport in the porous anode structure. The origin of the material electroactivity is revealed based on X‐Ray photoelectron spectroscopic analysis of pristine (as deposited), sodiated, and desodiated Si–O–C layers. The evaluation of the spectroscopic data indicates reversible activity of the material due to the complex contribution of carbon and silicon redox centers. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulation of LiClO4 solutions in sulfolane has been performed in a wide range of concentrations from 2 × 102 to 7 × 103 mol/m3 (7 M) using the Opslaa force field. It was found that the total coordination number (the sum of coordination numbers for sulfolane and perchlorate anion) of the lithium cation decreased with an increase in the lithium perchlorate concentration in solution from 5.7 to 4.5. It was shown that sulfolane solvates one lithium cation by one oxygen atom regardless of the salt concentration; but above the salt concentration 2 × 103 mol/m3 (2 M) (molar ratio of sulfolane/LiClO4 < 5), sulfolane acts as a bridging ligand between two lithium cations; the lithium perchlorate anion is coordinated with the lithium cation by one oxygen atom; only at the molar ratio sulfolane/LiClO4 = 1 (salt concentration 7 × 103 mol/m3) the perchlorate anion acts as a bridging ligand and is coordinated with several lithium cations at once. At a concentration of 2.35 × 103 mol/m3 (sulfolane/LiClO4 = 4), the structure of the first solvation shell of the lithium cation changes; the perchlorate anion is introduced in it, filling the vacancies in the coordination sphere that appear because of the lack of free sulfolane molecules. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐ion batteries (ZIBs) are a promising energy storage technology due to their intrinsic safety, eco‐friendliness, and cost‐effectiveness. However, aqueous electrolytes generally induce parasitic interfacial reactions (e.g., dendrite growth and passivation) that degrade the Zn metal anode, shortening ZIBs lifespan. This study develops a novel hydrated deep eutectic electrolyte (DEE), containing sulfolane (SL) and Zn(ClO4)2·6H2O, to prevent water‐induced deterioration. The strong coordination between SL and Zn2+ triggers the deep eutectic effect, extending the operating temperature window of the DEE. The unique water‐in‐DEE structure boosts ionic diffusion, promotes Zn2+ deposition, and reduces water reactivity, as revealed by in‐depth simulations and experiments. The developed DEE suppresses dendrite formation, allowing the Zn|DEE|Zn symmetrical cells to cycle over thousands of hours without short‐circuiting. With a polyaniline (PANI) cathode, Zn|DEE|PANI cells can cycle 2500 times with a capacity of 72 mAh g−1 at 3 A g−1 at room temperature and 500 times with 73 mAh g−1 at 0.3 A g−1 at −30 °C. The newly developed DEE significantly is a step forward for inexpensive, stable, and high‐performance ZIBs. [ABSTRACT FROM AUTHOR]

In this research, electro-Fenton method was used for removal and degradation of sulfolane in a petrochemical wastewater. It was selected as candidate because high solubility in water, chemical and thermal stability, low volatility and its difficult treatment. It was demonstrated that electro-Fenton method was carried out in a batch electrolytic reactor for degradation more than 97.5% sulfolane at time 60 min. The effect of operating conditions including current density, H2O2 dosage and pH of sample on the efficiency of process was investigated using response surface method. It was found the optimized conditions were current density 15 mA cm-2, H2O2 dosage 3% (v/v) and pH 2.5, although the pH has the most effect on removal efficiency. Furthermore, the consumption of energy, iron electrodes consumption, chemical oxygen demand (COD) and biochemical oxygen demand (BOD) removal and the amount of sludge produced during the application of this method were evaluated at optimum conditions. The COD and BOD removal were 55% and 43%, respectively. The degradation pathway of sulfolane by electro-Fenton as well as the transformation products was investigated using GC-FID, GC-MS, GC-SCD and total sulfur analyzer. The results demonstrated that the electro-Fenton was a feasible technique for degradation of sulfolane contaminated petrochemical wastewater. [ABSTRACT FROM AUTHOR]

The effect of lithium bis(oxalato)borate (LiBOB) on the physicochemical properties of lithium perchlolate solutions in sulfolane and the cycling time of lithium metal electrode is studied. It is found that the introduction of a small amount (0.24 M) of LiBOB into sulfolane solutions of LiClO4 increases insignificantly the solution viscosity but does not decrease the specific ion conductivity. The larger amounts of LiBOB decrease the electrolyte solution specific ion conductivity and increase both its viscosity and the activation energies of conductivity and viscous flow. The corrected conductivity of the solution containing two salts with the overall concentration 1.54 М is shown to far exceed the corrected conductivity of 1.5 М LiClO4 solution in sulfolane, which can be explained by the formation of ion associates of the higher order in the presence of LiBOB. The introduction of lithium bis(oxalato)borate into sulfolane solutions of lithium perchlorate increases the resistance of surface layers on the lithium metal electrode and the electrode cycling time. The main factor that determines the cycling time of lithium metal electrode is associated with protective properties of surface layers formed on the lithium electrode rather than with their conductivity. [ABSTRACT FROM AUTHOR]

Sulfolane is a solvent used in industrial refining with identified environmental exposure in drinking water. Due to potential large species differences, the National Toxicology Program (NTP) conducted 28-day toxicity studies in male and female Hsd:Sprague Dawley® SD® rats, B6C3F1/N mice, and Hartley guinea pigs. A wide dose range of 0, 1, 10, 30, 100, 300, and 800 mg/kg was administered via gavage. Histopathology, clinical pathology, and organ weights were evaluated after 28 days of exposure. In addition, plasma concentrations of sulfolane were evaluated 2 and 24 h after the last dose. Increased mortality was observed in the highest dose group of guinea pigs and mice while decreased body weight was observed in rats compared to controls. Histopathological lesions were observed in the kidney (male rat), stomach (male mice), esophagus (male and female guinea pigs), and nose (male guinea pigs). Plasma concentrations were generally higher in rats and guinea pigs compared to mice with evidence of saturated clearance at higher doses. Male rats appear to be the most sensitive with hyaline droplet accumulation occurring at all doses, although the human relevance of this finding is questionable.

Sulfolane is a solvent used in the petrochemical industry and a groundwater contaminant in areas near refineries. The current studies were conducted to assess the impact of oral exposure to sulfolane on the immune system using two models: (1) a perinatal drinking water exposure to 0, 30, 100, 300, or 1000 mg/L from gestation day (GD) 6 until ∼13 weeks-of-age in Harlan Sprague Dawley rats; and, (2) a 90-day gavage exposure of adult female B6C3F1/N mice to 0, 1, 10, 30, 100, or 300 mg/kg/day. Immune parameters evaluated included measurement of antibody production against sheep red blood cells (SRBC) and keyhole limpet hemocyanin (KLH), ex vivo measurements of natural killer (NK) cell activity, cytotoxic T-cell (CTL) activity, and T-cell proliferation, as well as measures of splenic immune cell populations, hematological parameters, and histopathology of immune tissues. A decrease in ex vivo NK cell activity was observed in cells from female – but not male – F1 rats following developmental exposure. In adult female mice, splenic NK cell number was lower than the vehicle controls at doses ≥ 100 mg/kg; however, ex vivo NK cell activity was not affected by sulfolane treatment. In female mice, a decrease in the number of large unstained cells at doses ≥ 30 mg/kg was observed. In F1 rats, effects on white blood cells (WBC) were limited to a decreasing trend in leukocytes in females; no effects were observed in males. Under the conditions of this study, a no-observed-effect level (NOEL) of 3 mg/kg/day was identified based on reduced NK cell activity in female F1 rats. Overall, these findings suggest that oral exposure to sulfolane in rodents had minimal effects on the immune system.

In this study, we aimed to evaluate the effect of sulfolane (SL) as a co-solvent in conventional carbonate-based electrolytes and its compatibility with a LiMn2O4 (LMO) cathode. The amount of SL was varied from 10 to 50 vol.% in an EC-DMC mixture (1:1 vol. ratio) within a 1.0-M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The thermal properties of the electrolytes were studied using thermogravimetric analysis (TGA). Solvent flammability was measured via self-extinguishing time (SET) and ignition time indexes while viscosity was gauged by the Ostwald method. Ionic conductivity was evaluated by electrochemical impedance spectroscopy (EIS). Electrochemical techniques such as cyclic voltammetry (CV) and galvanostatic cycling with potential limitation (GCPL) were carried out to evaluate battery performance with the selected electrolytes. The results indicated that an increasing proportion of SL leads to an enhancement of the thermal and oxidation stability of the electrolytes. At 20-vol.% SL and below, the as-synthesized electrolytes exhibited a high ionic conductivity of 7.45 mS.cm-1 (25oC) and enabled LMO to deliver a specific capacity of 103 mAh.g-1 with a capacity retention of 92% after 20 cycles at C/10 rate. Due to such favourable properties, SL can be used as a co-solvent in EC-DMC systems to enhance the safety of lithium-ion batteries under high voltage conditions.

Measurements of kinetics rates of CO2 in aqueous solutions of methyldiethanolamine (MDEA), piperazine (PZ), and mixtures of (MDEA + PZ), (PZ + sulfolane) and (MDEA + sulfolane) were carried out using the stopped flow technique, and reported in terms of pseudo‐first‐order rate constants (k0). When possible, the second‐order reaction rate constants (k2) were regressed from the data. Experiments were performed over new concentration ranges of (10–60), (200–800), (200–800, 10–40), (10–40, 10–200), and (200–800, 10–200) mol/m3 for the above‐mentioned five systems, respectively, and at temperatures varying from (298.15–313.15 K). When sulfolane was added to the amine solution, pseudo‐first‐order rate constants in the mixed solvents were higher than in aqueous MDEA and PZ solutions at all temperatures. The kinetic rates were highest at 298.15 K and decreased at higher temperatures for aqueous (MDEA + sulfolane) solutions but increased with temperature for aqueous (PZ + sulfolane) systems. Reaction orders for both PZ and MDEA were practically one at all sulfolane concentrations and temperatures. The base catalysis mechanism was used to regress very well data for aqueous MDEA and (MDEA + sulfolane + water) and the termolecular mechanism was used for (PZ + sulfolane + water) system. Both the zwitterion and termolecular models were able to fit the experimental data for the aqueous PZ system well. Finally, the termolecular and a hybrid model based on the combination of the Zwitterion and base catalysis mechanisms were able to successfully correlate the experimental data for the mixed aqueous (MDEA + PZ) systems. [ABSTRACT FROM AUTHOR]

The effect of the force field, atomic charges of sulfolane and perchlorate anion, and scale of ionic charges on the results of molecular dynamics (MD) simulation of the physicochemical properties of a 1 M LiClO4 solution in sulfolane was evaluated. The simulation was performed using the OPLS-AA, Amber (GAFF), Charmm, and Gromos force fields. The best correlation between the calculated and experimental physicochemical properties of the solution was obtained using the OPLS-AA force field, the atomic charges calculated by the B3LYP/aug-cc-pVTZ method, and with ionic charges scaled by 80% as default charges (±1.0). The coordination number of the lithium cation with respect to sulfolane was calculated: 5.3 with ionic charges scaled by 100% and 4.7 for 80%. It was shown that sulfolane is coordinated to the lithium cation by one oxygen atom of the sulfone group. [ABSTRACT FROM AUTHOR]

The effect of temperature (40, 50, 60, and 70°C) on the composition of solvate complexes of lithium perchlorate with sulfolane was studied by the method of automated vacuum gravimetry during isothermal evaporation of the solvent. It is found that the composition of the solvate complexes of lithium perchlorate with sulfolane is determined by the temperature of their formation. Raising the temperature lowers the number of sulfolane molecules in the solvate complex. A tetrasolvate of lithium perchlorate with sulfolane forms at 40°C, and disolvates form at 50, 60, and 70°C. The composition of solvate complexes of lithium perchlorate with sulfolane is also confirmed via thermogravimetry. It is assumed that the differences between the compositions of the solvate complexes in the lithium perchlorate–sulfolane system at different temperatures are due to differences in their structure. [ABSTRACT FROM AUTHOR]

The physico-chemical, electrochemical, and thermal properties of lithium bis(oxalate)borate solutions in sulfolane are studied. The sulfolane solutions of lithium bis(oxalate)borate were found to have lower specific ion conductivity and higher viscosity as compared with solutions of lithium perchlorate and lithium hexafluorophosphate. With an increase in the concentration of lithium bis(oxalate)borate solutions in sulfolane, the activation energies for ion conductivity and viscous flow increased. The association constant of lithium bis(oxalate)borate in sulfolane is lower than that of LiClO4 and close to LiPF6. From the dependence of the association constant on the donor number of lithium salts' anions, the donor number value of the [B(C2O4)]– anion was estimated as ~3. The effective transference number of lithium ion in 1 M lithium bis(oxalate)borate solution in sulfolane is 0.46 ± 0.03, which is higher than in 1 M LiClO4 solution (0.39 ± 0.02) and close to 1 M LiBF4 solution (0.42 ± 0.03) in sulfolane. The sulfolane solutions of lithium bis(oxalate)borate are shown to be prone to supercooling and thermodynamically nonequilibrium states formation. The anodic stability boundary of 1 M lithium bis(oxalate)borate solution in sulfolane is as high as 5.65 V vs. Li/Li+ reference electrode. According to the anodic stability, sulfolane solutions of lithium salts are ranked in the following order: LiPF6 ~ LiBF4 > Li bis(oxalate)borate ~ LiClO4 > LiSO3CF3. The cycling life of lithium metal electrode in lithium bis(oxalate)borate sulfolane solution is 1.75 times longer than that in LiClO4 solution; it is determined by the dispersion rate of lithium metal rather than by the electrolyte decomposition rate. [ABSTRACT FROM AUTHOR]

Sulfolane is a solvent used in the petrochemical industry and a groundwater contaminant in areas near refineries. The current studies were conducted to assess the impact of oral exposure to sulfolane on the immune system using two models: (1) a perinatal drinking water exposure to 0, 30, 100, 300, or 1000 mg/L from gestation day (GD) 6 until ∼13 weeks-of-age in Harlan Sprague Dawley rats; and, (2) a 90-day gavage exposure of adult female B6C3F1/N mice to 0, 1, 10, 30, 100, or 300 mg/kg/day. Immune parameters evaluated included measurement of antibody production against sheep red blood cells (SRBC) and keyhole limpet hemocyanin (KLH), ex vivo measurements of natural killer (NK) cell activity, cytotoxic T-cell (CTL) activity, and T-cell proliferation, as well as measures of splenic immune cell populations, hematological parameters, and histopathology of immune tissues. A decrease in ex vivo NK cell activity was observed in cells from female – but not male – F1 rats following developmental exposure. In adult female mice, splenic NK cell number was lower than the vehicle controls at doses ≥ 100 mg/kg; however, ex vivo NK cell activity was not affected by sulfolane treatment. In female mice, a decrease in the number of large unstained cells at doses ≥ 30 mg/kg was observed. In F1 rats, effects on white blood cells (WBC) were limited to a decreasing trend in leukocytes in females; no effects were observed in males. Under the conditions of this study, a no-observed-effect level (NOEL) of 3 mg/kg/day was identified based on reduced NK cell activity in female F1 rats. Overall, these findings suggest that oral exposure to sulfolane in rodents had minimal effects on the immune system. [ABSTRACT FROM AUTHOR]

Solid electrolytes may be the answer to overcome many obstacles in developing the next generation of renewable batteries. A novel composite solid electrolyte (CSE) composed of a poly(vinylidene fluoride) (PVDF) base with an active nanofiber filler of aluminum-doped garnet Li ceramic, Li salt lithium bis -(trifluoromethanesulfonyl)imide (LiTFSI), Li fluoride (LiF) stabilizing additive, and plasticizer sulfolane was fabricated. In a Li|CSE|LFP cell with this CSE, a high capacity of 168 mAh g -1 with a retention of 98% after 200 cycles was obtained, representing the best performance to date of a solid electrolyte with a PVDF base and a garnet inorganic filler. In a Li metal cell with Si and Li, it yielded a discharge capacity of 2867 mAh g -1 and was cycled 60 times at a current density of 100 mAh g -1 , a significant step forward in utilizing a solid electrolyte of any kind with the desirable Si anode. In producing this CSE, the components and fabrication process were chosen to have a lower cost and improved safety and environmental impact compared with the current state-of-the-art Li-ion battery.

In this work, a multifunctional 2m dual‐salt sulfolane (TMS)/ethyl acetate (EA)‐based localized high‐concentration electrolyte (LHCE) with 10 wt% fluorocarbonate (FEC) is reported. Its incorporation into a Li||Ni0.5Co0.2Mn0.3O2 battery enables it to maintain nearly 89% capacity retention after 200 cycles with 1 C (200 mA g−1) charge/discharge current density charged to 4.6 V at 25 °C, showing good high‐voltage cyclic stability. A superior 10 C high‐rate performance with 65% (≈130 mAh g−1) specific capacity is also achieved. Furthermore, it still remains a liquid and exhibits good ionic conductivity even at −80 °C, and enables Li||Ni0.5Co0.2Mn0.3O2 batteries to deliver more than 50% of their room‐temperature capacity at −40 °C and remains stable for over 200 cycles under the same condition as before, realizing outstanding low‐temperature fast‐charging/discharging performance. It also demonstrates compatibility with both lithium metal and graphite anode. All in all, this work provides a new idea for the design of a fast‐dynamic, high‐voltage, and low‐temperature lithium battery electrolyte. The findings of this work indicate that LHCEs made directly from the optimal high‐concentration electrolyte are not the most suitable approach, combining the diluent with an additive is necessary and effective. [ABSTRACT FROM AUTHOR]

Sodium metal anodes have attracted great attention for the development of a next generation of high-energy batteries because of their high theoretical capacity (1166 mAh·g−1), low redox potential (−2.71 V vs. SHE), and abundance. However, sodium reacts with most of the liquid electrolytes described to date and it has the shortcoming of dendrite formation during sodium deposition. Several strategies have been proposed to overcome these issues, including the incorporation of electrolyte additives. This work reports on the use of SO2 and sulfolane as additives in organic electrolytes to modify the sodium–electrolyte interphase, making the sodium plating/stripping process more robust. Not only is the process more stable in the case of sodium metal anodes, but also the use of copper substrates is enabled. In fact, high-quality sodium films on copper have been attained by adding small mole fractions of the additives, which paves the way for the development of anode-free batteries. In a general vein, this work stresses the importance of researching on compatible and cost-effective additives that can be easily implemented in practice.

• CO 2 solubility in a mixture of sulfolane and deep eutectic solvent (DES) was investigated. • DES is composed of choline chloride and methyldiethanolamine (MDEA) in a molar ratio of 1 to 6. • The vapor-liquid equilibrium of CO 2 was measured in a mixture of the present DES with Sulfolane • Gas solubility results were obtained at various temperatures and DES compositions. • PC-SAFT Equation of State was used to predict the phase behavior of DES+ sulfolane (Piperazine)+CO 2 systems. In recent years, releasing post-combustion CO 2 into the atmosphere has led to global warming. Air contamination has appeared as a challenge for governments, so several approaches have been used to overcome this issue. So far, physical and chemical solvents have been employed by researchers for CO 2 capture. These years deep eutectic solvents (DES) have emerged as an alternative to traditional solvents. In this study, we have investigated a mixture of DES + a physical solvent for the CO 2 solubility measurement using a static vapor-liquid equilibrium cell. In this work, the DES was composed of Choline Chloride and MDEA in a molar ratio of 1 to 6 which is blended with sulfolane in weight percentages of 5,10, and 15. We performed the experiments at temperatures of 323.15, 333.15, and 343.15 K and a pressure range of up to 5 MPa. In our previous work, we had already investigated the influence of piperazine on the present DES that led to enhancing CO 2 absorption in the mixture, while adding sulfolane to the DES in the present work does not present a positive effect on CO 2 solubility in the DES. Enhancing pressure and reducing temperature also led to increasing CO 2 solubility. Finally, we modeled the solubility data with the PC-SAFT equation of state. The modeling results were in excellent agreement with the experimental data for DES-CO 2 , DES-sulfolane-CO 2, and DES-piperazine-CO 2 systems, so the PC-SAFT EoS successfully estimated the carbon dioxide solubility in the present systems with the absolute average deviation percent of less than unity. [Display omitted] [ABSTRACT FROM AUTHOR]