Water in Protic Ionic Liquids: Properties and Use of a New Class of Electrolytes for Energy-Storage Devices.

In this work, the properties of "water-in-PIL" (PIL=protic ionic liquid) electrolytes are reported based on 1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr TFSI). Taking advantage of experimental and theoretical investigations, it is shown that the amount of water inside the electrolyte has a dramatic effect on the viscosity, conductivity, density, cation-anion interplay, and electrochemical stability of Pyr TFSI. The impact of water on the properties of this ionic liquid also affects its use as an electrolyte for electrochemical double-layer capacitors (EDLCs).

Mixtures of glyme and aprotic-protic ionic liquids as electrolytes for energy storage devices.

Ionic liquids (ILs) have been proven to be promising electrolytes for electrochemical energy storage devices such as supercapacitors and lithium ion batteries. In the last years, due to deficiency in storage of lithium on earth, innovative systems, such as sodium-based devices, attracted considerable attention. IL-based electrolytes have been proposed also as electrolytes for these devices.

Preface to Special Issue of ChemSusChem on Interfacing Experiment and Theory in the Development of Energy Storage and Devices.

This Editorial discusses the importance of scientists currently working in separate fields-experimental characterization of novel materials and theoretical investigations of electrochemical processes-joining forces to advance the field of energy-storage materials and devices. Some of these efforts are published in this Special Issue by ChemSusChem.

Glyoxal-Based Solvents for Electrochemical Energy-Storage Devices.

In this work an investigation about the use of the solvents 1,1,2,2-tetramethoxyethane, also called tetramethoxy glyoxal (TMG), and 1,1,2,2-tetraethoxyethane [also called tetraethoxy glyoxal (TEG)], which belong to the chemical family of carbonyl derivatives, as electrolyte components for electrical double layer capacitors (EDLCs) and lithium-ion batteries (LIBs) is reported for the first time. TEG and TMG are commercial solvents displaying a good set of properties, a low toxicity, and a low price. Although for EDLCs the use of these solvents does appear particularly appealing, their use in LIBs is certainly interesting.

Cell Concepts of Metal-Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications.

There is great interest in using sulfur as active component in rechargeable batteries thanks to its low cost and high specific charge (1672 mAh/g). The electrochemistry of sulfur, however, is complex and cell concepts are required, which differ from conventional designs. This review summarizes different strategies for utilizing sulfur in rechargeable batteries among membrane concepts, polysulfide concepts, all-solid-state concepts as well as high-temperature systems.

Anodic Dissolution of Al Current Collectors in Unconventional Solvents for High Voltage Electrochemical Double-Layer Capacitors.

This study investigated the anodic dissolution of Al current collectors in unconventional electrolytes for high voltage electrochemical double-layer capacitors (EDLCs) containing adiponitrile (ADN), 3-cyanopropionic acid methyl ester (CPAME), 2-methyl-glutaronitrile (2-MGN) as solvent, and tetraethylammonium tetrafluoroborate (Et NBF ) and tetraethylammonium bis(trifluoromethanesulfonyl)imide (Et NTFSI) as conductive salts. To have a comparison with the state-of-the-art electrolytes, the same salts were also used in combination with acetonitrile (ACN). The chemical-physical properties of the electrolytes were investigated.

From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises.

Mobile and stationary energy storage by rechargeable batteries is a topic of broad societal and economical relevance. Lithium-ion battery (LIB) technology is at the forefront of the development, but a massively growing market will likely put severe pressure on resources and supply chains. Recently, sodium-ion batteries (SIBs) have been reconsidered with the aim of providing a lower-cost alternative that is less susceptible to resource and supply risks.

Structural Investigations on Lithium-Doped Protic and Aprotic Ionic Liquids.

Solutions of lithium bis(trifluoromethanesulfonyl)imide (LiNTf), in four different [NTf]-based ionic liquids, are extensively investigated as potential electrolytes for lithium-ion batteries. Solvation of the [Li] ions in the ionic liquids and its impact on their physicochemical properties are studied herein with the aid of molecular dynamics simulations. The cationic components of the investigated liquids were systematically varied so as to individually evaluate effects of specific structural changes; increase in ring size, the addition of an alkyl chain and absence of an acidic proton, on the solvation and mobility of the [Li] cations.

Ionic Liquids in Lithium-Ion Batteries.

Lithium-ion batteries are among the most widespread energy storage devices in our society. In order to introduce these devices in new key applications such as transportation, however, their safety and their operative temperature range need to be significantly improved. These improvements can be obtained only by developing new electrolytes.

Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts.

The discharging and charging of batteries require ion transfer across phase boundaries. In conventional lithium-ion batteries, Li(+) ions have to cross the liquid electrolyte and only need to pass the electrode interfaces. Future high-energy batteries may need to work as hybrids, and so serially combine a liquid electrolyte and a solid electrolyte to suppress unwanted redox shuttles.

Graphene mediated improved sodium storage in nanocrystalline anatase TiO2 for sodium ion batteries with ether electrolyte.

We report here the synergistic effect of graphene and diglyme electrolyte in significantly improving the sodium insertion electrochemistry of nanocrystalline anatase TiO2.

Critical factors in sonochemical degradation of fumaric acid.

The effects of critical factors such as Henry's Law constant, atmospheric OH rate constant, initial concentration, H2O2, FeSO4 and tert-butanol on the sonochemical degradation of fumaric acid have been investigated. The pseudo first-order rate constant for the sonochemical degradation of 1mM fumaric acid is much lower than those for chloroform and phenol degradation, and is related to solute concentration at the bubble/water interface and reactivity towards hydroxyl radicals. Furthermore, fumaric acid is preferentially oxidized at the lower initial concentration.

From lithium to sodium: cell chemistry of room temperature sodium-air and sodium-sulfur batteries.

Research devoted to room temperature lithium-sulfur (Li/S8) and lithium-oxygen (Li/O2) batteries has significantly increased over the past ten years. The race to develop such cell systems is mainly motivated by the very high theoretical energy density and the abundance of sulfur and oxygen. The cell chemistry, however, is complex, and progress toward practical device development remains hampered by some fundamental key issues, which are currently being tackled by numerous approaches.

Hydroamination reactions of alkynes with ortho-substituted anilines in ball mills: synthesis of benzannulated N-heterocycles by a cascade reaction.

It was demonstrated that ortho-substituted anilines are prone to undergo hydroamination reactions with diethyl acetylenedicarboxylate in a planetary ball mill. A sequential coupling of the intermolecular hydroamination reaction with intramolecular ring closure was utilized for the syntheses of benzooxazines, quinoxalines, and benzothiazines from readily available building blocks, that is, electrophilic alkynes and anilines with OH, NH, or SH groups in the ortho position. For the heterocycle formation, it was shown that several stress conditions were able to initiate the reaction in the solid state.

Efficient mechanochemical complexation of various steroid compounds with α-, β- and γ-cyclodextrin.

Mechanochemical technology enables solvent-free micronized solid dispersions and efficient molecular host-guest inclusion complexes to be formed in matrices which contain cyclodextrins (CDs). This type of complexation has been studied using α-, β- and γ-cyclodextrin with the dual aims of improving overall solubility and enhancing the bioavailability of common steroid compounds, such as cholic acids and β-sitosterols or lowering cholesterol content in products of animal origin. Several parameters have been studied and optimized: CD/compound molar ratio (1:1, 1:2, 2:1 and 3:1) in function of the cavity sizes of the three different CDs, milling time (from 5 to 40 min) and rotation speed (from 100 to 300 rpm).

Scale-up of organic reactions in ball mills: process intensification with regard to energy efficiency and economy of scale.

The scale-up of the Knoevenagel-condensation between vanillin and barbituric acid carried out in planetary ball mills is investigated from an engineering perspective. Generally, the reaction proceeded in the solid state without intermediate melting and afforded selectively only one product. The reaction has been used as a model to analyze the influence and relationship of different parameters related to operation in planetary ball mills.

Thermal behavior of pinan-2-ol and linalool.

Linalool is an important intermediate for syntheses of isoprenoid fragrance compounds and vitamins A and E. One process option for its production is the thermal gas-phase isomerization of cis- and trans-pinan-2-ol. Investigations of this reaction were performed in a flow-type apparatus in a temperature range from 350-600 °C and a residence time range of 0.

Sonoelectrochemical degradation of phenol in aqueous solutions.

The sonoelectrochemical degradation of phenol in aqueous solutions with stainless steel electrodes and high-frequency ultrasound (850kHz) was investigated. A 60% synergetic effect was obtained in the combined reaction system. High concentration of electrolyte (sodium sulfate) and a high electrical voltage are favorable conditions for the degradation of phenol.

Degradation of carbamazepine in environmentally relevant concentrations in water by Hydrodynamic-Acoustic-Cavitation (HAC).

The antiepileptic drug carbamazepine is one of the most abundant pharmaceuticals in the German aquatic environment. The effect of low carbamazepine concentrations (1-50 μg L(-1)) is discussed controversially, but ecotoxicological studies revealed reproduction toxicity, decreased enzymatic activity and bioaccumulation in different test organisms. Therefore, as a preventive step, an efficient and cost-effective technique for wastewater treatment plants is needed to stop the entry of pharmaceuticals into the aquatic environment.

Microwave-assisted partial hydrogenation of citral by using ionic liquid-coated porous glass catalysts.

The microwave-assisted hydrogenation of citral (3,7-dimethylocta-2,6-dienal) to citronellal with molecular hydrogen as the reducing agent was investigated. Several polar and non-polar solvents were screened and imidazolium-based ionic liquids were applied as modifiers for the palladium-containing porous glass catalysts (Pd/TP). The best results were obtained with N-ethyl-N'-methylimidazolium dicyanamide, N-ethyl-N'-methylimidazolium acetate, or N-ethyl-N'-methylimidazolium trifluoroacetate, which were used to prepare supported catalysts with an ionic liquid layer (SCILL) on Pd/TP by wet-impregnation.

Fast, ligand- and solvent-free synthesis of 1,4-substituted buta-1,3-diynes by Cu-catalyzed homocoupling of terminal alkynes in a ball mill.

A method for the Glaser coupling reaction of alkynes by using a vibration ball mill has been developed. The procedure avoids the use of ligands and solvents during the reaction. Aryl- and alkyl-substituted terminal alkynes undergo homocoupling if coground with KF-Al(2)O(3) and CuI as a milling auxiliary and catalyst.

Enhanced effect of suction-cavitation on the ozonation of phenol.

800mL of 1.0mM phenol-containing aqueous solution was circulated at 20°C for 30 min in a suction-reactor, while 3.2 mg min(-1) ozone was introduced into the solution under the suction orifice.

Fast, ligand- and solvent-free copper-catalyzed click reactions in a ball mill.

A new, ligand- and solvent-free method for the Huisgen 1,3-dipolar cycloaddition (click reaction) was developed using a planetary ball mill. Besides various alkynes and azides, a propargyl functionalized polymer was converted by mill clicking. Moreover, it was possible to carry out a click polymerization in a ball mill.

Ball milling in organic synthesis: solutions and challenges.

During the last decade numerous protocols have been published using the method of ball milling for synthesis all over the field of organic chemistry. However, compared to other methods leaving their marks on the road to sustainable synthesis (e.g.