Room Temperature Ionic Liquids Research Articles

Room-temperature ionic liquid electrolytes for carbon fiber anodes in structural batteries

Structural batteries require thermally stable electrolytes paired with carbon fibers (CFs), which offer advantages of lightweight, high mechanical strength, and good electrical conductivity. This work evaluated various room-temperature ionic-liquids (RTILs) as compatible electrolytes for CF anodes and LiFePO4 (LFP) cathodes on CFs. This LFP/CF full-cell design eliminates Cu and Al current-collectors, potentially enhancing gravimetric energy and reducing costs. Among various RTILs, LiTFSI in N-propyl-N-methylpyrrolidinium (PYR13) – bis(fluorosulfonyl)imide (FSI) offered promising LFP/CF full-cell performances, attributed to the formation of solid electrolyte interphase (SEI) layer on the CF anode with components such as Li2Sx, Li2S–SO3, LiF, LixFy and F–SO2, identified through X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analyses further confirmed the electrochemical stability of the SEI layer on CF anodes. The LFP/CF cell delivered an initial capacity of 119 mAh/g and relatively high Coulombic efficiency when using the 1 M LiTFSI in PYR13-FSI. CF cycled in different electrolytes exhibit varying mechanical properties with up to 10.08 % loss in tensile strength, which may be related to CF surface degradation during cycling. The 1 M LiTFSI in PYR13-FSI is non-flammable, offering a significant thermal safety. This work successfully demonstrated the significant potential of 1 M LiTFSI in PYR13-FSI RTILs, which enables the use of CF as both an anode active material and cathode current collector for structural battery applications.

Miniaturized Electrochemical Gas Sensor with a Functional Nanocomposite and Thin Ionic Liquid Interface for Highly Sensitive and Rapid Detection of Hydrogen.

Hydrogen has been widely used in industrial and commercial applications as a carbon-free, efficient energy source. Due to the high flammability and explosion risk of hydrogen-air mixtures, it is vital to develop sensors featuring fast-responding and high sensitivity for hydrogen leakage detection. This paper presents a miniaturized electrochemical gas sensor by elaborately establishing a nanocomposite and thin ionic liquid interface for highly sensitive and rapid electrochemical detection of hydrogen, in which a remarkable response time and recovery time of approximately 6 s was achieved at room temperature. A screen-printed carbon electrode was modified with a reduced graphene oxide-carbon nanotube (rGO-CNT) hybrid and platinum-palladium (Pt-Pd) bimetallic nanoparticles to realize high sensitivity. To achieve miniaturization and high stability of the sensor, a thin-film room-temperature ionic liquid (RTIL) was employed as the electrolyte with a significantly decreased response time. The fast-responding hydrogen sensor demonstrates excellent performance with high sensitivity, linearity, and repeatability at concentrations below the lower explosive limit of 4 vol %. The engineered high-performance interface and gas sensor provide a promising and effective strategy for gas sensor design and rapid hazardous gas monitoring.

Specimen preparation for atom probe tomography

Abstract In the past 20 years or so, atom probe tomography has gone from a niche technique in physical metallurgy to a well-established method in many parts of materials science and beyond. This is owing to the improvement in both instrumentation and specimen preparation. Given the availability of instruments, successful specimen preparation is often the bottleneck in atom probe projects. In this article, the authors want to give an overview of the types of preparation techniques that are available and which challenges they pose. This includes basic electropolishing, which was dominant until the introduction of focused ion beam-based preparation some 25 years ago. Nowadays, focused ion beam-based preparation methods possibly represent the largest share, as they allow for site-specific specimen preparation, non-conductive specimens and often a higher throughput. They are continuously improved, i. e., through higher current plasma ion columns, cryo preparation for sensitive materials and room temperature liquids and ‘additive’ techniques for nanomaterials. This steadily increases the types of materials that can be analyzed using atom probe tomography.

Untapping the coal reserves: Green desulfurization using phosphonium based ionic liquids

Thar coalfields of Pakistan are the 16th largest lignite coal reserves in the world. This untapped fuel source has high density for energy production. However, sulfur content limits its cleaner use the present research is a green practice for desulfurization of bituminous and lignite coal. For this purpose tetrabutylphosphonium hydroxide with anions precursor perchloric acid, dimethyl sulfate, and trifloromethanesulfonic acid was refluxed separately at room temperature to produce tetrabutylphosphonium trifloromethanesulfonate [P4444+][CF3SO3−], tetrabutylphosphonium perchlorate [P4444+][ClO4−], and tetrabutylphosphonium methyl sulfate [P4444+][MeSO4−]. The synthesized acidic nature phosphonium based room temperature ionic liquids (PRTILs) were characterized using standardized analytical techniques of FTIR, 1H NMR, 13C NMR, HPLC and TGA/DSC. TD50 order of PRTILs was 47 ºC< 253 ºC < 292 ºC for [P4444+][CF3SO3−], [P4444+][ClO4−], [P4444+][MeSO4−] respectively. The proximate and ultimate analysis of coal samples from Balochistan coal field indicated low moisture and high carbon content along with gross calorific value of 6938–7589 Kcal/Kg. The coal samples from Shahrig and Sor-range coal mines with highest sulfur content (6.9–11.8 %) were selected for desulfurization procedures by using PRTILs and assessed through FTIR, HPLC and CHNS analyzer. The solvents were found more effective in removal of thiophene, benzothiophene, and dibenzothiophene in an oxidative environment along with an increase of GCV of coal samples to 7204–7792 Kcal/Kg. The regeneration of spent PRTILs for three cycles in 25 % ethanol reveal them as sustainable solvents for the coal desulfurization process.

Tough and temperature-resistant mask-based separator realized by K-β”-Al2O3 protective layer for stabilizing NaK liquid metal batteries

The development of low-cost, high-temperature-resistant separators is crucial for optimizing the reaction interface and improving the safety performance of liquid NaK metal batteries. This paper presents a novel separator with a solid electrolyte layer, Mask@40 %β-Al2O3, primarily composed of K-β”-Al2O3 known for its exceptional ionic conductivity and high-temperature resistance. Specifically designed for room-temperature liquid NaK metal batteries, the Mask@40 %β-Al2O3 separator effectively transforms the unstable liquid–liquid interface between liquid NaK metal electrodes and traditional organic electrolytes into a stable solid–liquid interface. This transformation prevents short-circuiting caused by area collapse under high-temperature conditions. Moreover, the Bare Mask component can adsorb a conventional organic electrolyte to construct a stable solid–liquid interface on the cathode side, thereby reducing the typically observed high interfacial resistance associated with conventional solid electrolytes. The cost-effective nature and simple preparation process of the Mask@40 %β-Al2O3 separator address cost concerns while presenting an encouraging new direction for applying room-temperature liquid NaK metal batteries in extreme conditions.

Flipping Water Orientation at the Surface of Water-in-Salt and Salt-in-Water Solutions.

Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air. Our results show that, under salt-in-water conditions, the orientation of the OH group hydrogen-bonded to the other water molecules flips from the OH group pointing down into the liquid for pure water to up due to the accumulation of anions in the cation-rich interfacial region. However, under the water-in-salt condition, the interfacial water molecules are confined by RTIL, and their orientation is down. Details of the water organization depend critically on the alkyl chain length of the imidazolium cation. Our results demonstrate that the surface structure can be tuned by altering the molecular structure and concentration of the RTIL.

Relationship between structure and properties of bio-based aromatic ionic liquids for tribological applications

This study examined six phosphonium-based room-temperature ionic liquids (PRTILs) having trihexyltetradecyl- or tributyltetradecyl-phosphonium cations with saccharinate, salicylate, or benzoate anions, and obtained a feature parameter to correlate their cationic chain length, anionic ring size, and contact angle with tribological properties. PRTILs with trihexyltetradecyl-phosphonium cations had lower coefficient of friction (COF) and wear than PRTILs with tributyltetradecyl- phosphonium cations, a trend attributed to the additional methylene groups providing lower contact angle. For either cation, PRTILs with the saccharinate anion exhibited much lower COF and wear than single-ring anions, due to the formation of a low-shear-strength-tribofilm facilitated by the double-ring structure and sulfur of saccharinate. Overall, this study revealed PRTIL interfacial mechanisms that can be used to identify anion-cation combinations with optimal tribological performance.

The Role of Asymmetry of Perfluoro anion in Ionic Liquids: From Basic Physical Properties to the Application in Lithium Batteries

Room-temperature ionic liquids (RTILs) have attracted significant attention as non-volatile, non-flammable electrolytes over the past three decades. While the synthesis of cationic species is relatively well-established through the quaternization reaction of tertiary amines, the synthesis of perfluoro anions is much more difficult, resulting in a more limited variety compared to cations. In this study, we explore the influence of anionic species on both fundamental properties, such as thermal properties and transport properties, and on the performance of lithium-ion batteries, particularly their rate capabilities. Furthermore, we highlight how novel anionic species not only improve the properties of RTILs but also lead to the development of unique electrolyte systems, such as organic ionic plastic crystals and medium-low temperature lithium molten salts. Through our research results, we would like to demonstrate the importance of developing new anionic species from fundamental studies to practical applications in RTILs.

Physicochemical and Thermal Behaviors of Room-Temperature Phosphonium Ionic Liquids Based on Fluorosulfonyl(trifluoromethylsulfonyl)Amide Anion As Potential Electrolytes

The physicochemical properties of novel room-temperature ionic liquids based on quaternary phosphonium cations in combination with asymmetric fluorosulfonyl(trifluoromethylsulfonyl)amide anion were reported. It was found that such phosphonium ionic liquids showed lower melting points than those of the conventional amide anion-based ionic liquids. Typical density and transport property behaviors for ionic liquids were observed. Several phosphonium ionic liquids based on fluorosulfonyl(trifluoromethylsulfonyl)amide anion exhibited low viscosities. The phosphonium ionic liquids based on fluorosulfonyl(trifluoromethylsulfonyl)amide anion exhibited relatively low thermal stability when compared to the corresponding conventional amide anion-based ionic liquids.

Selective Co(II) and Ni(II) Separation Using the Trihexyl(tetradecyl)phosphonium Decanoate Ionic Liquid

The room temperature ionic liquid trihexyl(tetradecyl)phosphonium decanoate ([P66614][Dec]) was employed in the liquid-liquid extraction of Co(II) from hydrochloric acid solutions in the presence of Ni(II). The extraction performance in liquid-liquid separations showed a strong dependence on the acid content of the feed aqueous solution. The best performance in terms of extracted cobalt and selectivity was obtained when the feed contained a HCl concentration above 6 M On the contrary, when the experiment was performed in absence of HCl, a lower extraction and Co/Ni selectivity were obtained. This behavior has been rationalized by considering the protonation of the [Dec]− anion and the different Co(II)/Ni(II) speciation in HCl media. Moreover, polymer inclusion membranes (PIMs) were prepared using PVC and [P66614][Dec] at different weight rations. Only the PIM formulated with a 30:70/PVC:[P66614][Dec] weight ratio demonstrated effective extraction of Co(II) from the HCl solution. The extraction efficiency and selectivity of the PIM was comparable to that from biphasic liquid experiments at 8 M HCl. The results of this study constitute a promising background for further practical developments of carboxylate-based ILs applied in Co/Ni separations.

Understanding the effect of alkyl chain on extraction of Np4+ and Pu4+ with hexaalkyl nitrilotriacetamides into an ionic liquid vis-à-vis a molecular solvent

Extraction of actinides using exotic ligands in room temperature ionic liquids is one of the most preferred areas of research these days. Though the amides are well studied for the extraction of actinides from nitric acid feeds, multiple amides (such as tripodal amides) are of recent origin, and reports on solvent extraction with these ligands in room temperature ionic liquids are very rare. In this work, the extraction of Np4+ and Pu4+ was studied with a series of N,N,N′,N′,N″,N″-hexaalkyl nitrilotriacetamides (NTAamides) in an ionic liquid with an objective to understand the effect of the alkyl chains length on their extraction ability. Bumim⋅Tf2N was chosen as ionic liquid due to its favourable viscosity for distribution studies. The extraction of tetravalent actinides Np4+ and Pu4+ increased linearly with increasing the alkyl chain of the NTAamides from n-butyl via n-hexyl to n-octyl. The extraction pattern was surprisingly opposite to the most observed extraction patterns in an ionic liquid, where the extraction generally decreases sharply upon increasing the feed acidity. The extracted species were ascertained as M(NO3)5⋅L (LH), where M = Np4+ or Pu4+, for each ligand. Consequent to the formation of an entirely divergent extracted complex, the extraction pattern is completely different than that expected in an ionic liquid.

Room-Temperature Liquid Crystalline Tetraphenylethylene-Surfactant Complex with Chiral Supramolecular Structure and Tunable Circularly Polarized Luminescence.

A novel room-temperature liquid crystal of tetraphenylethylene derivative (TPE-DHAB) was synthesized using an ionic self-assembly strategy. The TPE-DHAB complex exhibits typical aggregation-induced emission properties and a unique helical supramolecular structure. Moreover, the generation and handedness inversion of circularly polarized luminescence (CPL) can be achieved through further chiral solvation, providing a facile approach to fabricate room-temperature liquid crystalline materials with controllable supramolecular structures and tunable CPL properties through a synergistic strategy of ionic self-assembly and chiral solvation process.

Investigation of PVDF‐co‐HPF based ultrafiltration polymer inclusion membrane for the extraction of cadmium ions

AbstractUltrafiltration polymer inclusion membranes (UPIMs) have become increasingly significant for the separation and purification of heavy metals from industrial wastes and wastewater due to their convenience compared to other liquid membranes. A novel process for cadmium separation and recovery has been developed using biodegradable ion carriers, specifically room temperature ionic liquids with various molecular structures. This innovation has greatly enhanced the efficiency and application of UPIMs for cadmium separation, while also providing the membranes with unique functional properties. In this study, various UPIMs were produced using polyvinyl fluoride hexafluoropropylene (PVDF‐co‐HPF) as the base polymer, different plasticizers, and symmetric room temperature ionic liquids as ion carriers. The ability of these membranes to extract cadmium ions was evaluated, demonstrating a removal rate of 9.70 μmol s−1 from a 25 ppm Cd(II) solution under optimum conditions. The selectivity and stability of the optimized UPIM were examined under different conditions to obtain a deeper insight into of its performance. The morphological characteristics of the optimized UPIM were examined using scanning electron microscopy and atomic force microscopy techniques.

Recent Advances in Synthesis and Applications of Organic Ionic Saltsbased Sensor Arrays

Abstract: Sensor arrays contain a group of sensors, improve observations with new dimensions, provide better estimations, and additional parameters in comparison to the individual selective sensor. The array-based sensing technique provides good performance to respond to various gaseous or liquid analytes. Room temperature ionic liquids (RTILs) (melting point &lt;25oC) and Group of uniform materials based on organic salts (GUMBOS) (melting point =25-250oC) are organic ionic salts, composed of an oppositely charged pair of bulky organic cations and bulky organic/inorganic anion and shows interesting tunable physicochemical properties. In this review article, we will discuss the sensing performance of ILs- and GUMBOS-based sensor arrays. ILs-based sensor arrays have been used in electrochemical gas sensing, solvent discrimination, colorimetric gas sensing, sensing of organic compounds, optoelectronic sensing of vapors and solutions, and vapour sensing through IL/QCM systems. GUMBOS-based sensor arrays have been employed in vapour sensing through the GUMBOS/QCM method, detection, and discrimination of proteins.

Imminent prognosis for piperazinium-based ionic liquids applications for coal desulfurization

Sulfur is one of the most important quality parameters for coal rank and utility in power generation. Combustion of coal having high sulfur content leads to SOx emissions which have detrimental impacts on the environment and human health. For sulfur remediation, N-methyl piperazinium-based room temperature ionic liquids (RTILs) were synthesized with two acidic anions precursors’ dimethyl sulfate and Perchloric acid. These novel RTILs were characterized using standardized analytical techniques of FTIR, 1H NMR, 13C NMR, HPLC, and TGA/DSC. Thermal stability of dimethyl piperazinium methyl sulfate [DMPI+][MeSO4−] and methyl piperazinium perchlorate [MPI+][ClO4−] was 284 °C and 256 °C. The proximate and ultimate analysis of coal samples collected from block II of the Thar coal field shows high moisture content (29–47 %) and gross calorific value between 5006–6660 Btu/lb suggesting it is Lignite-B type fuel. Total sulfur content in coal samples was 1–4.1 % reflecting variable degree of sulfurization. Coal cleansing through oxidative extractive desulfurization theme using nifty combinations of these acidic RTILs was verified by HPLC, FTIR, CHNS Elemental Analyzer, and X-ray Florescence (XRF) techniques. Sulfur leaching from the coal matrix was higher for methyl piperazinium perchlorate and an 85 % decrease in the sulfur part of coal along with increased heat content through this study suggests cleaner and sustainable use of coal.

Effects of Heterogeneous Mixing of Imidazolium-Based Ionic Liquids with Alcohols on Complex Formation of Ni(II) Ion.

Understanding the complex formation of metal ions in room-temperature ionic liquids (ILs) is essential for the application of ILs in solvent extraction. Nevertheless, the research on metal complex formation in ILs lags behind other applications. The complex formation equilibria may be influenced by specific interactions among the metal ion, ligand molecule, and IL cation and anion. In the present investigation, the complex formation of Ni2+ with ethanol (EtOH) and methanol (MeOH) molecules in ILs, 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([CNmim][TFSA], where N represents the alkyl chain lengths of 2 and 8) was discussed in terms of the microscopic interactions among alcohol molecules, [CNmim]+ and [TFSA]-, and the mesoscopic mixing states of alcohols in [CNmim][TFSA], with N = 2-12. The microscopic interaction of alcohol molecules with the imidazolium ring H atoms in the ILs was evaluated by using ATR-IR and 1H and 13C NMR spectroscopies. The self-hydrogen bonding of alcohol molecules was clarified from the O-H stretching vibration of alcohol molecules. MeOH molecules can be more strongly hydrogen-bonded with themselves than EtOH molecules due to the less steric hindrance and the weaker dispersion force of MeOH with the IL cation's alkyl chain. In fact, small-angle neutron scattering (SANS) experiments revealed the more heterogeneous mixing of MeOH with the ILs by the self-hydrogen bonding among MeOH molecules than EtOH. The longer the IL cation's alkyl chain, the more the MeOH clusters significantly form. In contrast, the formation of EtOH clusters becomes weaker with elongating the alkyl chain. Ultraviolet (UV)-visible spectroscopic measurements on Ni2+-[CNmim][TFSA]-alcohol solutions with N = 2 and 8 revealed that di-, tetra-, and hexa-alcohol-Ni2+ complexes are formed in both the ILs. With N = 2, the stabilities of Ni2+-EtOH and Ni2+-MeOH complexes are comparable in the IL. However, with N = 8, the complexes are more stable in the EtOH solutions than in the MeOH solutions. This is because the less heterogeneous mixing of EtOH molecules with the IL results in the larger enthalpic contribution in the complex formation, as shown by the thermodynamic parameters estimated by the van't Hoff plots on the stability constants at several temperatures.

Yttrium Separation from Phosphorite Extract Using Liquid Extraction with Room Temperature Ionic Liquids Followed by Electrochemical Reduction

Yttrium Separation from Phosphorite Extract Using Liquid Extraction with Room Temperature Ionic Liquids Followed by Electrochemical Reduction

Revelation of room temperature liquid crystallinity and yellow-orange electroluminescence (EQE>7%) in a columnar self-assembled N-annulated perylene bisimide

The synthesis of highly fluorescent compounds is a critical necessity to facilitate cost-effective and metal-independent production of organic light-emitting diodes (OLEDs). This investigation introduces a readily soluble, electron-deficient N-annulated perylene bisimide (PBI-NST) equipped with a swallow tail, exhibiting room temperature columnar oblique mesophase with a low clearing point and high photoluminescence quantum yield, positioning it as a promising candidate for efficient OLEDs. Leveraging the luminescent properties of PBI-NST, a series of OLED devices were fabricated with PBI-NST as the sole emitter and at various concentrations in CBP host material. Impressively, doped devices employing the compound at 0.5 wt% emitter within the host material CBP displayed an exceptional external quantum efficiency (EQE) of 7.2 %, accompanied by a luminance of 2689 cd/m2. Further, a voltage dependent emission tuning was also noticed. The notable increase in EQE is mainly attributed to the contributions of hybrid local and charge transfer (HLCT) and triplet–triplet annihilation (TTA) process. The substantial enhancement in EQE marks a significant advancement in the application of multifunctional columnar self-assembled materials for OLED development.

Effect of Structural Modification in β Diketone on the Mutual Separation of Nd and Pr into Room-Temperature Ionic Liquid

Effect of Structural Modification in β Diketone on the Mutual Separation of Nd and Pr into Room-Temperature Ionic Liquid

Flexible Aluminum-Air Batteries

Wearable and flexible electronics have a wide range of applications. Making a flexible power source for them is essential. Aluminum-air batteries are attractive for powering portable, lightweight devices due to their inexpensive, light, and powerful energy source. In this project, the Al-air battery was made using activated carbon and aluminum electrodes, chloride-based electrolytes with ionic liquid additives. Various mixtures of 1-ethyl-3-methylimidazolium chloride, aluminum chloride, sodium hydroxide, and sodium chloride were studied. Fundamental properties of room-temperature ionic liquids, such as lower conductivity and density, improved the performance of aluminum-air batteries. Cell capacity, cyclic voltammetry behavior, and cell interfacial impedance with various electrolytes were optimized using the design of experiments. The battery's electrical power output and cell capacity were lower than those obtained using an activated carbon air cathode. The cell capacity over repeated electrochemical reactions was stable. The Al-air battery had regular cyclic voltammetry behavior. Aluminum hydroxide was not found on the anode electrode when an ionic liquid electrolyte was used. The interfacial cell impedance did not decrease after electrochemical reactions over a long time.