Search Results (45)

For various applications, particularly in battery technology, there is a significant demand for uniform, high-quality lithium or lithium-coated materials. The use of electrodeposition techniques to obtain such materials has not proven practical or economical due to the low solubility of most lithium salts in suitable solvents. In this study, we propose efficient lithium electrodeposition processes and baths that can be operated at low temperatures and relatively low costs. We utilized organic solvents such as dimethyl acetamide (DMA), dimethylforamide (DMF), and dimethyl sulfoxide (DMSO), as well as a mixture of DMSO and ionic liquid [1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide BMIMTFSI]. Lithium salts such as LiCl, Li₂CO₃, and LiNO₃ were tested. Lithium metal was deposited on copper substrates at different temperatures and selected current densities within an argon-filled glovebox using a DC power source or a PARSTAT-4000A potentiostat. Cyclic voltammetry (CV) was employed to determine and compare the deposition processes. The obtained deposits were analyzed through visual inspection (photography) and scanning electron microscopy (SEM). Chemical analysis (ICP-OES) and XRD confirmed the presence of lithium and occasionally lithium hydroxide in the deposits. The best results were achieved with the deposition of lithium from DMSO-LiNO₃ and DMSO-BMIMTFSI-LiNO₃ systems. Full article

Multifunctional materials requiring low functional voltages are the main goal of new industrial smart technologies. Polypyrrole (PPy) was chemically synthesized by a simple dip-coating process on glucose–porcine skin gelatin nanofibers, accelerating mass production, here shown on nanofiber scaffolds (NFs) with those consisting of composites. The isometric and isotonic characterizations by electro-chemo-mechanical deformation (ECMD) of NFS-PPy are obtained from cyclic voltammetric and chronoamperometric responses in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium triflouromethanesulfonate (LiTF) and sodium perchlorate (NaClO₄) in propylene carbonate (PC). The results indicate a prevalent anion-driven actuation of the linear actuator (expansion by oxidation and contraction by reduction). Different stress (4–2 kPa) and strain (0.7–0.4%) gradients are a function of the anion Van der Waals volume. During reversible actuation (expansion/contraction), the material stores/releases energy, obtaining greater specific capacitance, 68 F g⁻¹, in LiTFSI solutions, keeping 82% of this capacity after 2000 cycles. The sensitivity (the slope of the linear sensing equation) is a characteristic of the exchanged anion. The reaction of the PPy-coated nanofiber is multifunctional, developing simultaneous actuation, sensing, and energy storage. The materials were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. Full article

The electrochemical properties of the hydrophobic room-temperature ionic liquid 1-propyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide (PMMIm(TFSI)) were investigated, for the first time, using an electrochemical double-layer capacitor-mimicking cell containing two identical-sized micro–mesoporous molybdenum carbide-derived carbon electrodes (MMP-C(Mo₂C)), by applying cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Surprisingly, despite the substitution of the slightly acidic hydrogen atom with a methyl group at the carbon atom located between two nitrogen atoms in the imidazolium cation, the EIS and CV measurements demonstrated that PMMIm(TFSI) began to decompose electrochemically at the same cell potential (ΔE) as 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIm(BF₄)), specifically at ΔE = 2.75 V. However, the CV and EIS data indicated that PMMIm(TFSI) decomposed with a significantly lower intensity than EMIm(BF₄). Therefore, we believe that the use of PMMIm(TFSI) as the electrolyte will enable the construction of safer supercapacitors that can tolerate short periods of over-polarization up to ΔE = 4.0 V. However, when the ΔE ≤ 3.2 V was applied, EMIm(BF₄) offered higher maximum power compared to PMMIm(TFSI). We found that the calculated maximum gravimetric power precisely describes the maximum ΔE applicable for a supercapacitor candidate. Full article

The addition reactions of water, alcohols, and primary and secondary amines to the 10-acetonitrilium derivative of nido-carborane were studied. Hydrolysis of 10-MeC≡N-7,8-C₂B₉H₁₁ results in iminol 10-MeC(OH)=HN-7,8-C₂B₉H₁₁, which, on treatment with a base, gives amide [10-MeC(=O)HN-7,8-C₂B₉H₁₁]⁻. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with alcohols lead to imidates 10-ROC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et) as mixtures of E- and Z-isomers. In the solid state, 10-MeOC(Me)=HN-7,8-C₂B₉H₁₁ adopts E-configuration. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with primary amines result in amidines 10-RNHC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et) as mixtures of E- and Z-isomers. In the solid state 10-EtNHC(Me)=HN-7,8-C₂B₉H₁₁ was found to have the Z-configuration, which is stabilized by intramolecular N-H⋯H-B interactions between the NH group originating from the primary amine and the BH group of the carborane cage. These interactions are rather strong (3.7 kcal/mol) and are likely to persist in solution. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with secondary acyclic (Me₂NH, Et₂NH) and cyclic (piperidine, morpholine) amines result in amidines 10-R₂NC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et; R₂ = N(CH₂)₅, N(CH₂CH₂)₂O) as single isomers, which, according to single crystal X-ray diffraction data, have the E-configuration. Full article

The present article describes the successful performance of crossed aldol reactions of the CF₃-containing pseudo-C₂ symmetric cyclic imide with various aldehydes. The utilization of HMPA as an additive attained the preferential formation of the anti-products in good to excellent yields, which contrasts with our previous method without this additive, proceeding to furnish the corresponding syn-isomers. The effective participation of ketones and α,β-unsaturated carbonyl compounds in reactions with this imide was also demonstrated to expand the application of this imide. Full article

This research explores the enhancement of electrochemical performance in magnesium batteries by optimising magnesium alloy anodes, explicitly focusing on Mg-Al and Mg-Ag alloys. The study’s objective was to determine the impact of alloy composition on anode voltage stability and overall battery efficiency, particularly under extended cycling conditions. The research assessed the anodes’ voltage behaviour and internal resistance across magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)₂) electrolyte formulations using a systematic setup involving cyclic voltammetry on the anode and electrochemical impedance spectroscopy. The Mg-Al alloy demonstrated superior performance, with minimal voltage drop and lower resistance increase than the Mg-Ag alloy. The results showed that the Mg-Al alloy maintained over 85% energy efficiency after 100 cycles, significantly outperforming the Mg-Ag alloy, which exhibited increased degradation and efficiency reduction to approximately 80%. These findings confirm that incorporating aluminium into magnesium anodes stabilises the anode voltage and enhances the overall battery efficiency by mitigating degradation mechanisms. Consequently, the Mg-Al alloy is identified as an up-and-coming candidate for use in advanced battery technologies, offering energy density and cycle life improvements. This study lays the groundwork for future research to refine magnesium alloy compositions further to boost battery performance. Full article

Cyclic acid anhydride is a not very widespread structure in nature, but with a determining role in natural products possessing this functionality in their skeleton. To the best of our knowledge, no revision of terpenes containing cyclic anhydrides has been previously reported. The result was that more than 100 terpenic cyclic anhydrides and related compounds were found to be in need of being reported. This review has been systematically organized by terpene skeletons, from the smallest to largest, describing their sources and bioactivities. In addition, different biosynthetic pathways for their final oxidations, namely, routes A, B and C, leading to the formation of these heterocyclic natural products, have been proposed. We have also included the most plausible precursors of these natural products, which mostly happened to be present in the same natural source. Some molecules derived from terpene cyclic anhydrides, such as their natural imide derivatives, have also been described due to their significant biological activity. In this sense, special attention has been paid to cantharidin because of its historical relevance and its broad bioactivity. A plausible biosynthesis of cantharidin has been proposed for the first time. Finally, cyclic anhydride structures that were firstly assigned as anhydrides and later corrected have been also described. Full article

Prediction of the antibacterial activity of new chemical compounds is an important task, due to the growing problem of bacterial drug resistance. Generalized linear models (GLMs) were created using 85 amidrazone derivatives based on the results of antimicrobial activity tests, determined as the minimum inhibitory concentration (MIC) against Gram-positive bacteria: Staphylococcus aureus, Enterococcus faecalis, Micrococcus luteus, Nocardia corallina, and Mycobacterium smegmatis. For the analysis of compounds characterized by experimentally measured MIC values, we included physicochemical properties (e.g., molecular weight, number of hydrogen donors and acceptors, topological polar surface area, compound percentages of carbon, nitrogen, and oxygen, melting points, and lipophilicity) as potential predictors. The presence of R1 and R2 substituents, as well as interactions between melting temperature and R1 or R2 substituents, were also considered. The set of potential predictors also included possible biological effects (e.g., antibacterial, antituberculotic) of tested compounds calculated with the PASS (Prediction of Activity Spectra for Substances) program. Using GLMs with least absolute shrinkage and selection (LASSO), least-angle regression, and stepwise selection, statistically significant models with the optimal value of the adjusted determination coefficient and of seven fit criteria were chosen, e.g., Akaike’s information criterion. The most often selected variables were as follows: molecular weight, PASS_antieczematic, PASS_anti-inflam, squared melting temperature, PASS_antitumor, and experimental lipophilicity. Additionally, relevant to the bacterial strain, the interactions between melting temperature and R1 or R2 substituents were selected, indicating that the relationship between MIC and melting temperature depends on the type of R1 or R2 substituent. Full article

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li₆PS₅F_0.5Cl_0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries. Full article

An environmentally friendly and sustainable approach was adopted to produce a molecularly imprinted polymer (MIP) via electropolymerization, with remarkable electrochemical sensing properties, tested in tyrosine (tyr) detection. The 2,2′-bis(2,2′-bithiophene-5-yl)-3,3′-bithianaphtene (BT₂-T₄) was chosen as functional monomer and MIP electrosynthesis was carried out via cyclic voltammetry on low-volume (20 μL) screen-printed carbon electrodes (C-SPE) in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BMIM) TFSI). An easy and rapid washing treatment allowed us to obtain the resulting MIP film, directly used for tyr electrochemical detection, carried out amperometrically. The sensor showed a linear response in the concentration range of 15–200 μM, with LOD of 1.04 µM, LOQ of 3.17 μM and good performance in selectivity, stability, and reproducibility. Tyrosine amperometric detection was also carried out in human plasma, resulting in a satisfactory recovery estimation. The work represents the first use of BT₂-T₄ as a functional monomer for the production of a molecularly imprinted polymer, with a green approach afforded by using a few microliters of a room temperature ionic liquid as an alternative to common organic solvents on screen-printed carbon electrodes, resulting in a valuable system that meets the green chemistry guidelines, which is today an essential criterion in both research and application field. Full article

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young’s modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10⁻⁶ S·cm⁻¹ at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10⁻⁵ S·cm⁻¹ and further increases to 10⁻³ S·cm⁻¹ in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries. Full article

Electrolytes play a critical role in battery performance. They are associated with an increased risk of safety issues. The main challenge faced by many researchers is how to balance the physical and electrical properties of electrolytes. Gel polymer electrolytes (GPEs) have received increasing attention due to their satisfactory properties of ionic conductivity, mechanical stability, and safety. Herein, we develop a gel network polymer electrolyte (GNPE) to address the challenge mentioned earlier. This GNPE was formed by tri-epoxide monomer and bis(fluorosulfonyl)imide lithium salt (LiFSI) via an in situ cationic polymerization under mild thermal conditions. The obtained GNPE exhibited a relatively high ionic conductivity (σ) of 2.63 × 10⁻⁴ S cm⁻¹, lithium transference number (t_Li⁺, 0.58) at room temperature (RT), and intimate electrode compatibility with LiFePO₄ and graphite. The LiFePO₄/GNPE/graphite battery also showed a promising cyclic performance at RT, e.g., a suitable discharge specific capacity of 127 mAh g⁻¹ and a high Coulombic efficiency (>97%) after 100 cycles at 0.2 C. Moreover, electrolyte films showed good mechanical stability and formed the SEI layer on the graphite anode. This study provides a facile method for preparing epoxy-based electrolytes for high-performance lithium-ion batteries (LIBs). Full article

In this study, we successfully synthesized a novel triacid monomer by means of the thermal cyclization reaction. Subsequently, a series of nitrogen-rich (A₃+B₂)-type fluorinated hyperbranched poly(amide-imide)s (denoted as PAI-1 and -2, respectively) were prepared by means of a one-pot method using this triacid monomer and a diamine monomer with a triphenylamine-carbazole unit as precursors. The degree of support of the prepared hyperbranched PAIs was found to be about 60% via ¹H NMR calculations. Through X-ray photoelectron spectroscopy (XPS), it was found that the binding energies of C-N (398.4 eV) and -NH (399.7 eV) became lower under a current, while the binding energy peak of N⁺ appeared at 402.9 eV. In addition, the PAIs have good solubility and thermal stability (T_gs: 256–261 °C, T_10%: 564–608 °C). Cyclic voltammetry (CV) analysis shows that the hyperbranched PAI films have good redox properties, and a range of values for the HOMO (4.83 to 4.85 eV) versus LUMO (1.85 to 1.97 eV) energy levels are calculated. The PAI films have excellent electrochromic properties: PAI-1 on coloration efficiency (CE) and transmittance change (ΔT, 852 nm) are 257 cm²/C and 62%, respectively, and have long-lasting redox properties (100 cycles). In addition, we conduct iodine adsorption tests using the structural features of PAIs with electron-drawing units, and the results show that PAI-1 had a high adsorption capacity for iodine (633 mg/g). Full article

This study investigates three carbide-derived carbon (CDC) materials (TiC, NbC, and Mo₂C) characterized by uni-, bi-, and tri-modal pore sizes, respectively, for energy storage in both neat and acetonitrile-diluted 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A distribution of micro- and mesopores was studied through low-temperature N₂ and CO₂ adsorption. To elucidate the relationships between porosity and the electrochemical properties of carbon materials, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy measurements were conducted using three-electrode test cells. The ultramicroporous TiC-derived carbon is characterized by a high packing density of 0.85 g cm⁻³, resulting in superior cathodic and anodic capacitances for both neat ionic liquid (IL) and a 1.9 M IL/acetonitrile electrolyte (93.6 and 75.8 F cm⁻³, respectively, in the dilute IL). However, the bi-modal pore-sized microporous NbC-derived carbon, with slightly lower cathodic and anodic capacitances (i.e., 85.0 and 73.7 F cm⁻³ in the dilute IL, respectively), has a lower pore resistance, making it more suitable for real-world applications. A symmetric two-electrode capacitor incorporating microporous CDC-NbC electrodes revealed an acceptable cycle life. After 10,000 cycles, the cell retained approximately 75% of its original capacitance, while the equivalent series resistance (ESR) only increased by 13%. Full article

Photochemical properties of symmetrical pyromellitic diimide containing two cymantrenyl fragments at two nitrogen atoms were studied with IR, NMR, UV-vis, ESI-MS, and cyclic voltammetry. It was found that new unstable chelates are formed during photolysis. At the same time, the CO ligand dissociates from two Mn(CO)₃ fragments during photoexcitation, which dramatically changes the electronic and redox properties of the molecule compared to the cymantrene derivative containing one imide fragment. Photolysis leads to a color change from light yellow to green. DFT calculations confirmed the possibility of the formation of complexes due to the loss of one or two CO ligands from manganese atoms. The results obtained with variation of photolysis conditions demonstrated the hemilabile character of the Mn-O=C(imide) bond. On addition of external ligands, the color and electrochemical properties changed, which is promising for the use of this complex as a sensor for small molecules. Full article