Ether Chains Research Articles

Tunable Cluster Luminescence and High Quantum Yield in Amine-Modified Maleic Anhydride Polymers.

Cluster luminescent materials (CLgens) with nonconjugated structures have attracted considerable attention. However, their low quantum yield and limited emission wavelengths, which are confined to the blue-green spectrum, continue to restrict their applicability. In this study, maleic anhydride polymer chains were modified with N-tristyrylene-1,2-diamine (TPM-NH2), creating a secondary donor-acceptor structure through freely rotatable phenyl groups and amino-anhydride interactions. This modification facilitated the formation of charge transfer (CT) states and strengthened the through-space interaction (TSI), resulting in a remarkable red shift in emission wavelength from 400 to 640 nm. The flexible ethyl chain acted as a bridging unit within this framework, enhancing through-space charge transfer (TSCT) and elevating the quantum yield (QY) to 28.28%. This research offers a strategy for improving the QY of anhydride copolymers and demonstrates the potential for controllable emission wavelengths, thereby broadening their application domains, including in light-conversion agricultural films.

Multi-stimuli actuation of a photoresponsive azobenzene based molecular switch.

There has been considerable interest in building switching functions into self-assembled monolayers with switching actuated by external stimuli such as light, electrical current, heat, pressure or chemical changes. In this study, dual switching functionality has been built into azobenzene based molecular monolayers. Switching behaviour has been compared for unsubstituted azobenzene monolayer adsorbates and two other monolayers whose ortho position on the terminal phenyl group is substituted by ethyl and isopropyl chains, respectively. The dual molecular switching functionality with light or protonation actuation is compared. EGaIn contacts to the monolayers have been used to record the J-V curves and characterize the on/off switching. This is complemented with further characterization by transition voltage spectroscopy (TVS), ultraviolet photoelectron spectroscopy (UPS), water contact angle determination, atomic force microscopy (AFM) and theoretical computations. It is concluded that side chains (the ethyl and isopropyl groups) are able to decouple neighbouring azobenzene adsorbates which promotes the photo-efficiency of isomerisation and switching. In addition, acid treatment is also applied to these three molecular layers to try to achieve dual stimuli actuation. The absorption wavelength of the azobenzene moiety red shifts by ∼100 nm for all the three protonated molecules. In the case of the unsubstituted azobenzene, its triggering wavelength is totally reversed once it is protonated. A logic truth table has been constructed for the SAM device, which shows that the simple azobenzene molecular layers exhibit the behaviour of an 'AND' logic gate which uses blue light and acid as two inputs.

Effect of ether introduction and ether chain length on electrochemical stability window feature of imidazolium ionic liquids with different anions: experimental and DFT studies

Effect of ether introduction and ether chain length on electrochemical stability window feature of imidazolium ionic liquids with different anions: experimental and DFT studies

Interaction between the Polyelectrolytes Unfractionated Heparin and Universal Heparin Reversal Agents.

The interaction of unfractionated heparin (UFH) with universal heparin reversal agent 7 (UHRA-7) is investigated. UHRA-7 is composed of a hyperbranched polyglycerol core onto which an array of methylated tris(2-aminoethylamine) (Me-TREN) charged groups is grafted, which in turn are shielded with a layer of small chain poly(ethylene glycol) methyl ether (mPEG) chains. This system has previously been shown to be biocompatible and to be effective at neutralizing heparin. The binding constant Kb was determined from isothermal titration calorimetry experiments, at temperatures ranging from 278 to 323 K and salt concentrations ranging from 0.06 to 0.20 M NaCl. The data were analyzed in terms of a number of different theoretical models to determine the contribution of counterion release and water release to driving the interaction between UFH and UHRA-7. With the support of NMR and molecular dynamics simulation data, a model of the interaction between UFH and UHRA-7 is proposed. The binding of heparin and universal heparin reversal agent 7 is mainly due to charge-charge interactions between the negatively charged units on UFH with positively charged Me-TREN and mPEG chains.

Thermal Conductivity in Side-Chain Liquid-Crystal Epoxy Polymers: Influence of Mesogen Structure.

Side-chain liquid-crystal epoxy polymers (SCLCEPs) are valued for their unique properties, which combine LC side chains with epoxide-based polyether main chains for ordered molecular arrangements. They have high thermal conductivity and optical properties due to their low polydispersity and high crystallinity. Achieving optimal thermal conductivity in SCLCEPs involves addressing factors such as mesogen nature, polymer design, and alignment within the polymer structure. Balancing these factors enhances their suitability for heat dissipation in advanced materials. In this study, SCLCEPs with a polyethylene glycol backbone and laterally arranged mesogens are synthesized via anionic ring opening of mesogenic epoxides with unique LC phases. These monomers, which feature biphenyl mesogens attached to glycidyloxy ether and different alkyl chain lengths on the other side, is designed to facilitate mesogen self-assembly and interaction. The resulting polymers exhibited higher crystallinity and LC phases than the monomers. Notably, because of their LC nature, their thermal conductivity exceeds 0.48 W·m-1 K-1 and increases with shortened alkyl chain lengths, reaching 0.57 W·m-1 K-1. This research expands the applications of SCLCEPs in advanced fields requiring enhanced thermal properties.

Ether chain-modified Alkanolguanidine for CO2 capture and subsequent conversion

Capturing CO2 and converting it into valuable chemicals has attracted considerable attention in recent years. Herein, a kind of ether chain-modified alkanolguanidines (ECMAs) was designed and synthesized as a dual functional reagent for carbon dioxide capture and conversion. Due to the presence of basic sites and CO2-philic ether chains, these ECMAs demonstrated almost equimolar CO2 capture at room temperature and atmospheric pressure through the synergy of physical and chemical absorption. Even for diluted CO2 (15 % CO2), 0.7 mol CO2 per mole capture reagent can still be achieved, showing their potential application in post-combustion capture. The synthesized ECMAs can also serve as catalyst in the cycloaddition reaction of CO2 with various epoxides, affording 75–99 % yield of corresponding cyclic carbonates under 3 MPa CO2 with tetrabutylammonium iodide (TBAI) as co-catalyst. Moreover, these ECMAs can be applied to the integrated CO2 capture and conversion, in which the ECMAs can react with CO2, forming the alkyl carbonate zwitterion as active CO2 species in the capture step. And in the subsequent cycloaddition reaction with propylene oxide, 52 % yield of propylene carbonate was obtained.

Spectroscopic Studies of Cation Structure Dependence on Lithium-Ion Conductivity in Phosphonium Ionic Liquid Electrolytes

1. Introduction In recent years, there has been active progress towards transitioning to electric vehicles (EVs) with the aim of realizing a carbon-neutral society, resulting in intensified development of lithium-ion secondary batteries (LIBs) with higher energy density. However, commercially available electrolytes for LIBs, while having a wide electrochemical window, often exhibit high volatility, posing a risk of fire hazard during thermal runaway. Ionic liquids (ILs) are promising materials as alternative electrolytes because of their excellent properties such as flame retardance, volatility resistance, and wide potential window.In our laboratory, we have focused on quaternary phosphonium-based ILs, which show higher electrochemical stability compared to common ILs such as imidazolium, pyrrolidinium, and ammonium, and evaluated them as electrolytes for LIBs.1) As a result, by optimizing the cation structure, we have found that ILs derived from trimethylphosphine can achieve relatively high-rate charge-discharge capability.2) In this study, we aimed to clarify the effect of the phosphonium cationic structure of ionic liquids on discharge rate characteristics. 2. Experimental Bis(fluorosulfonyl)amide (FSA)-based phosphonium ILs, triethyl(buthyl)phosphonium FSA (P2224-FSA) and triethyl(ethoxymethyl)phosphonium FSA (P222(2O1)-FSA), were dried by heating and stirring at over 80 °C for 24 h under vacuum. Then lithium salt (LiFSA) was added to these ILs (0.2–1.5 mol dm–3).Electrochemical measurements were conducted using a two electrodes half-cell. The cell was assembled using Li metal and graphite as the positive and negative electrodes, respectively, with a separator between them. The charge–discharge tests were conducted at 303 K in a constant current (CC) mode between 0 and 1.5 V (vs. Li metal). For the discharge rate test condition was followings, the charge condition was fixed at 0.05 C, and the discharge conditions were set to 0.05 C, 0.5 C, 1 C, 2 C, and 5 C. Self-diffusion coefficients of Li+, phosphonium and FSA– were determined by PGSTE-NMR. The conductivities were determined by an ac impedance measurement using a two Au-electrode cell. Raman spectra of the ILs were measured by micro-Raman spectroscopy featuring a continuous-wave green laser at room temperature (293 K). 3. Results and discussion Fig. 1 shows the results of the discharge rate test with phosphonium ILs electrolytes. Although the discharge capacity of P2224-FSA decreased with increasing the C-rate, P222(2O1)-FSA, which includes an ether structure, maintained high discharge capacity even at high-rate conditions In this study, we investigated the spectroscopic behavior of phosuphonium ILs for clarifying their ionic conduction mechanism.The self-diffusion coefficients, ionic transfusion numbers and conductivities of each C Li + = 1 M ILs are listed in Table 1. Despite the higher self-diffusion coefficients of the respective ions in P222(2O1)-FSA than in P2224-FSA, there was no significant difference between each IL’s ionic conductivity.Raman spectroscopy was used to evaluate the interaction between Li+ and FSA–. Fig. 2 shows the Raman spectra of C Li + = 1.5 M P2224-FSA and P222(2O1)-FSA. Two peaks appear around 1,220 cm–1 and 1,230 cm–1, which originate fromfree FSA– and Li+-boundFSA, respectively.3) The intensity ratio of these bands tended to change with IL cation species. The ratio derived from free FSA– was greater for P222(2O1)-FSA than for P2224-FSA. These results suggested that the structure of phosphonium affected Li+ solvation of phosphonium ILs. 4. Conclusions We found that the phosphonium cation with an ether chain weakens the FSA– solvation to Li+. This suggests that desolvation of part of the FSA– might occur due to the interaction of the ether chain with Li+. In ILs based on phosphoniums with ether chains, the ILs cationic structure might more influence on the Li+ conduction mechanism than in phosphonium ILs whiout ether chain. Acknowledgments This study was supported by a Grant-in-Aid for Scientific Research (B) from JSPS, Japan. This work was partly supported by a project, Gear of Education and Advanced Resourced (Gear 5.0). References 1) Tsunashima and M. Sugiya, Electrochem. commun., 9, 2353–2358 (2007).2) Matsumoto et al., SSRN Electron. J., (2023).3) Fujii, et al., J. Phys. Chem. C, 117, 19314−19324 (2013). Figure 1

An Unwanted Guest in the Electrochemical Oxidation of High-Voltage Li-Ion Battery Electrolytes: The Life of a Superacidic Proton

Lithium-ion batteries (LIBs) are central to the urgent societal need to decarbonize both transportation and energy storage on the grid. Unfortunately, despite their attractive energy/power density and high coulombic efficiency, further improvement of this technology – especially their durability – is desperately needed. To support these efforts, our study focuses on fundamental understanding of the decomposition pathways for LIB electrolytes at the cathode-electrolyte interface (CEI), as the nature of these reactions directly controls the extent to which cell capacity and voltage decays in these systems. In this study, we employ electrochemical methods, coupled with product analysis using NMR spectroscopy and mass spectrometry, to determine the decomposition mechanisms for a model electrolyte (1.3 M LiClO4 in EC) and demonstrate the impact of these mechanisms on technologically relevant systems (1.0 M LiPF6 in EC/EMC). Remarkably, we discover the electrochemical formation of superacidic protons, which provides a unified origin for a myriad of side reactions in every individual component of the CEI. In particular, electrochemically generated protons chemically catalyze EC decomposition into CO2 and other short and long chain ethers. They also react with LiPF6 to form the weaker acid HF and are involved in a direct acid-base reaction with the cathode active material, causing the leaching of transition metals into the electrolyte. Collectively, the results of this study all point to the urgent need to either mitigate this proton formation or introduce benign harvesting additives via new electrolyte design strategies.___________________The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan

Space-Confined Synthesis of Thinner Ether-Functionalized Nanofiltration Membranes with Coffee Ring Structure for Li+/Mg2+ Separation.

Positively charged nanofiltration membranes have attracted much attention in the field of lithium extraction from salt lakes due to their excellent ability to separate mono- and multi-valent cations. However, the thicker selective layer and the lower affinity for Li+ result in lower separation efficiency of the membranes. Here, PEI-P membranes with highly efficient Li+/Mg2+ separation performance are prepared by introducing highly lithophilic 4,7,10-Trioxygen-1,13-tridecanediamine (DCA) on the surface of PEI-TMC membranes using a post-modification method. Characterization and experimental results show that the utilization of the DCA-TMC crosslinked structure as a space-confined layer to inhibit the diffusion of the monomer not only increases the positive charge density of the membrane but also reduces its thickness by ≈35% and presents a unique coffee-ring structure, which ensures excellent water permeability and rejection of Mg2+. The ion-dipole interaction of the ether chains with Li+ facilitates Li+ transport and improves the Li+/Mg2+ selectivity (SLi,Mg=23.3). In a three-stage nanofiltration process for treating simulated salt lake water, the PEI-P membrane can reduce the Mg2+/Li+ ratio of the salt lake by 400-fold and produce Li2CO3 with a purity of more than 99.5%, demonstrating its potential application in lithium extraction from salt lakes.

Ellipsoidal micelle formation of quaternary ammonium salt-based gemini surfactants: structural analysis through small-angle X-ray scattering.

Gemini surfactants exhibit better adsorption and aggregation properties than those of monomeric surfactants. However, to enhance the functional properties of gemini surfactants, the effect of spacer structures on their aggregation behavior must be elucidated. Small-angle X-ray scattering (SAXS) has been performed to study the aggregate structures of monomeric surfactants, but its application has not been expanded to the analysis of gemini surfactants. Therefore, in this study, we performed a structural analysis of aggregates formed by quaternary ammonium salt-based gemini surfactants with different spacer structures in aqueous solutions through viscosity, dynamic light scattering (DLS), and SAXS measurements. We also investigated the effects of the spacer structure and surfactant concentration on the aggregation behavior. The DLS results indicated that gemini surfactants with spacers containing cyclic structures, such as diethylene and triethylene chains, formed small micelles (several nanometers in size) at the limiting concentration for dissolution in water. In contrast, gemini surfactants with nitrogen and oxygen atoms at the center of the spacer formed ellipsoidal micelles at low concentrations, as shown by SAXS results. The core and overall radii of the minor and major axes of the ellipsoidal micelles decreased with increasing surfactant concentration and were larger for spacers with two ethylene chains connected to central nitrogen and oxygen atoms than for spacers with rigid diethylene and ethylene chains connected to a central nitrogen atom.

Novel suppressor for damascene copper electrodeposition: Thioether-modified polyether with enhanced adsorption through an adjustable synthesis strategy

The void-free deposition of small-sized and high-aspect ratio interconnect structures requires stronger suppressors than conventional polyethers. In this work, thioether was introduced into polyether to develop novel suppressors with improved adsorption on electrode. The structure of thioether-modified polyether can be easily tailored by choosing proper polyether and thiol compound, thus providing a simple way to regulate electrochemical properties of the suppressor. The electrochemical and copper filling performance related to the molecular structure of novel suppressors were systematically investigated. Thioether-modified polyether, which retains the strong polarizability of typical suppressor and exhibits high resistance to accelerator desorption, can significantly suppress copper deposition on feature sidewalls. This enabled defect-free filling of narrower features at a concentration much lower than the typical usage concentration of suppressor. The modified polyethers with ethylene-propylene-ethylene (EPE) oxide triblock ether chains exhibited higher polarization strength and concentration dependence, facilitating the higher deposition current at the bottom during filling. The length and block ratio of ether chain further influenced the anti-desorption ability of the modified polyether, thereby impacting their suppression on sidewalls, which is crucial in filling process. The convenient structural adjustments for thioether-modified polyether, combined with the derived structure-property relationship, contribute to the development of new suppressors with strong adsorption performance.

Analysis of the effects of Pr1-xCexCoO3/dolomite catalyst on energy saving and carbon reduction in biomass gasification for the production of hydrogen-rich syngas

Biomass is considered a renewable green coal, and its clean and efficient utilization is of great significance for energy conservation and carbon reduction. One of the most critical aspects of biomass gasification is the selection of an appropriate catalyst. In this study, we synthesized a catalyst with 10 % Pr1-xCexCoO3 supported on dolomite using the sol-gel method. We conducted graded internal circulation gasification experiments to produce hydrogen-rich syngas. The effects of element substitution in PrCoO3, temperature, catalyst composition, and steam injection rate on the products were investigated. The optimal gasification conditions were determined through response surface regression analysis. The data indicate that this catalyst can improve gasification efficiency, with Pr0.4Ce0.6CoO3/Dol showing the best catalytic performance. It effectively reduces the required gasification temperature and steam amount, decreases CO2 production, and increases CO and H2 yields. The catalyst accelerates the cleavage and ring-opening reactions of hydrocarbons, leading to terminal chain hydroxylation, followed by the dehydration-condensation of methyl groups into ethers. As the temperature rises, the rate of carboxyl group removal gradually exceeds the rate of carboxyl group formation via the oxidation of hydroxyl and ether chains, resulting in an initial increase and then a decrease in the number of carboxyl groups. Under optimal gasification conditions, CO2 production is reduced by one-fourth compared to using a dolomite catalyst.

Effect of ether chain and isomerism on surface and antimicrobial activity of mono- and dicationic imidazolium-based surface-active ionic liquids

A series of 16 imidazolium-based surface-active ionic liquids (SAILs) were synthesized. The designed SAILs, consisted of either one amphiphilic center, 3-alkoxymethyl-1-benzylimidazolium or 3-alkoxymethyl-1-benzyl-2-methylimidazolium, and two amphiphilic centers, 3,3′-[α,ω-(dioxaalkane)]bis(1-benzylimidazolium) or 3,3′-[α,ω-(dioxaalkane)]bis(1-benzyl-2-methylimidazolium). These compounds were investigated in terms of thermal analysis, ability to self-organize to micelles, and antimicrobial activity. The insertion of an ether moiety in the alkyl side or spacer chain favored adsorption at the air–water interface and micellization in the bulk solution when compared to commercial chloride surfactants. The results showed that attachment of a methyl group to the imidazolium ring led to lower the critical micelle concentration (CMC) than lengthening the alkyl chain or spacer in the imidazolium cation. Additionally, biological activity increased with increasing hydrophobicity of the compounds. The methylation of the imidazole ring at positions 2 and 2′ yielded in a notable increase in bacteriostatic activity, especially against Gram-positive bacteria, notably the Staphylococcus aureus strains. It has been demonstrated that minor structural modifications, specifically substituting the imidazole ring instead of elongating the alkyl chain or spacer, can modify the micellization and aggregation behavior, leading to differences in both the efficacy and variety of antimicrobial activity of amphiphilic SAILs.

Ether chain modified electrochromic polymer based on EDOT and benzene

Polar side chain plays an critical role in regulating molecular aggregation, film morphology and electrochromic properties of conjugated polymer. Here an ether chain modified conjugated polymer poly(EB-ether) based on EDOT and benzene was prepared at low oxidation potential by electrochemical method in EtOH-CH2Cl2 (v/v = 5/1) containing 0.1 M Bu4NPF6. The prepared poly(EB-ether) could achieve similar electrochromic parameters with alkoxy chain modified poly(EB-alkoxy), such as optical contrast of 35 %, response time of 0.8 s, coloration efficiency of 283 C−1 cm2, and reversible color change between dark red and blue. Electrochromic results indicate that high-performance poly(EB-ether) film could be prepared in mixed solvent containing little CH2Cl2. Therefore, the introduction of ether chain in precursor is a feasible method to decrease or avoid the use of halogenated solvent in electrochemical polymerization process of precursor.

Cd-Ln (Ln = Pr, Sm, Yb and Nd) heteronuclear complexes based on the linear chain ether Schiff base: Structural regulation and fluorescence properties

Four structurally different Cd-Ln heteronuclear complexes based on the linear chain ether Schiff base ligand (bis(3-methoxysalicylidene)-3-oxapentane-1,5-diamine (H2L) and the co-ligands 4,4′-bipyridine (bipy) or isonicotinate (IN), with composition [PrCd2L2(CH3COO)2](NO3)·CH2Cl2 (1), {[SmCdL(bipy)(NO3)3]·CH2Cl2·CH3CH2OH}n (2), [YbCdL(IN)(NO3)(CH3COO)]n (3) and {[Nd2Cd2L2(IN)2(NO3)2(CH3OH)2(CH3COO)](NO3)}n (4), have been synthesized by interfacial diffusion methods. Structural regulation is achieved by changes in the co-ligands or Ln(III) ions of different radii: Single crystal X-ray analysis determined that 1 is a trinuclear cluster with the Pr(III) ion as a joint bridging of two CdL coordination units; 2 and 3 are both infinite one-dimensional zigzag coordination polymers consisting of CdLnL secondary units through coordination bridging bipy or IN; 4 is a two-dimensional graphene laminate structure formed by two types of CdNdL secondary units bridged by both IN and acetate simultaneously. In the solid state, the complexes 1–4 all exhibit fluorescence peaks based on H2L with blue shift and enhancement. The order of fluorescence peaks intensity of the complexes in N,N-dimethylformamide (DMF) solution is consistent with that in the solid state. Moreover, the corresponding characteristic emissions of Sm(III) ion in complex 2 can be observed in the fluorescence spectra in either solid state and DMF solution, indicating that [CdL] unit is suitable for the sensitization of Sm(III) ion.

Phenolic syringyl end groups in 13C-enriched hardwoods detected and quantified by solid-state NMR

While syringyl units are the most abundant monolignols in hardwood lignin, their phenolic (i.e. hydroxyl) end group concentration has not been measured. In two uniformly 13C-enriched young hardwoods, from beech and oak, the syringyl units were quantitatively investigated by advanced solid-state 13C NMR. Small signals of OH-terminated syringyl units were resolved in spectrally edited two-dimensional 13C–13C NMR spectra of the two hardwoods. Their distinct peak positions predicted based on literature data were validated via the abundant OH-terminated syringyl units in hydrolyzed 13C-beechwood. In a two-dimensional 13C–13C exchange spectrum with diagonal-ridge suppression, a well-resolved peak of phenolic syringyl units was observed at the characteristic C–H peak position of syringyl rings, without significant overlap from guaiacyl peaks. Accurate 13C chemical shifts of regular and end-group syringyl units were obtained. Through spectrally edited 2D NMR after 1H inversion recovery, phenols of condensed tannin complexed with arginine were carefully analyzed and shown to overlap minimally with signals from phenolic syringyl units. The local structure and resulting spin dynamics of ether (chain) and hydroxyl (end-group) syringyl units are nearly the same, enabling quantification by peak integration or deconvolution, which shows that phenolic syringyl end groups account for 2 ± 1 % of syringyl units in beechwood and 5 ± 2 % in oakwood. The observed low end-group concentration needs to be taken into account in realistic molecular models of hardwood lignin structure.

A Tale of Two Tails: Rotational Spectroscopy of N-Ethyl Maleimide and N-Ethyl Succinimide.

Broadband microwave spectra of N-ethyl maleimide (NEM) and N-ethyl succinimide (NES) have been recorded using chirped pulse Fourier transform microwave spectroscopy in the Ka-band (26.5-40 GHz). The spectra for both molecules were fit to a Watson A-reduced Hamiltonian in the Ir representation to obtain best fit experimental rotational constants (NEM: A0 = 2143.1988(29), B0 = 1868.7333(22), C0 = 1082.98458(36); NES: A0 = 2061.47756(14), B0 = 1791.73517(12), C0 = 1050.31263(11)), centrifugal distortion constants, and nuclear quadrupole coupling constants. While the heavy atoms of the five-membered ring of both molecules are planar, the ethyl chain has its terminal methyl group perpendicular to the ring. Along the relaxed potential energy curve for the ethyl dihedral angle (θ1 = C(6)-C(5)-N-C(4)), the ethyl group experiences significant steric strain when it is in the plane of the ring, associated with the interaction of the ethyl group with the two carbonyl oxygens. This leads to calculated barriers of θ1 = 1469 cm-1 and θ1 = 1680 cm-1 in N-ethyl maleimide and N-ethyl succinimide, respectively.

Unlocking the Use of LiCl as an Inexpensive Salt for Lithium-Ion Batteries with a Novel Anion Receptor.

Lithium chloride (LiCl) is an inexpensive and environmentally friendly salt abundant in the ocean. However, the insolubility of LiCl in conventional electrolyte solvents prevents the practical use of LiCl for lithium-ion batteries. Here, we report a novel method to increase the solubility of LiCl in a conventional electrolyte. The solubility of LiCl in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1/1, v/v) is about quadrupled by adding a small amount of anion receptor with two urea moieties as recognition sites connecting with an ether chain. Anion receptor is an organic molecule that can associate with anions. Our anion receptor is able to associate with chloride anion. The ionic conductivity of LiCl in EC/DMC increased from 0.023 mS cm-1 (without an anion receptor) to 0.075 mS cm-1 (with a 0.05 M anion receptor). The electrolyte in the presence of a 0.05 M receptor exhibits higher ionic conductivity, rate capability, and cyclability than the electrolyte without the receptor.

Multi-functionalization and recycling of basalt fibre/polypropylene laminated composites based on mixed plain-woven fabric and related interfacial decorations

The development of laminated composites of thermoplastic polypropylene (PP)/continuous basalt fabric is limited by poor mutual infiltration and weak interfacial interactions between the matrix and fabric, as well as the intrinsic flammability and susceptibility of the PP matrix to ultraviolet (UV) aging. To solve the above shortcomings in a high-efficiency manner, a multi-functional transition layer was constructed between the PP matrix and long basalt fibres (LBFs) based on a hybrid plain-woven fabric composed of LBFs weft yarns and PP warp yarns. After hot-laminating these hybrid plain-woven prepregs, the mechanical performance of the resultant laminates was optimised and strengthened by selecting the compositions of the multi-functional transition layers (comprising flexible alkyl glycidyl ether chains, various rigid inorganic nanoparticles, or a flexible-rigid hybrid layer). Among these different transition layers, the interface between the LBFs-g-MWCNTs-OH and the PP matrix presented better mutual infiltration due to the lower interfacial energy, stronger mechanical engagement effect derived from the rougher fibre surface, and higher interfacial modulus. Therefore, the fewer structural defects and more effective transfer of the applied load at the interface caused the tensile strength/modulus and flexural strength/modulus of the related hybrid weaving laminates (HWLs) to reach 278.1 MPa/31.8 GPa and 264.2 MPa/12.4 GPa, respectively. The rigid interfaces formed by the deposited nanoparticles also accelerated heat transfer from the matrix to the fibre and the absorption of UV-light inside composite, then improving the flame-retardancy and anti-UV aging performances of the corresponding HWLs. Finally, recyclability evaluations indicated that the waste LBFs-g-SiO2/PP HWLs can be used as anti-UV aging and flame-retardant agents to fabricate new modified PP pellets with multiple functions.

Impact of Glyme Ether Chain Length on the Interphasial Stability of Lithium-Electrode in High-Capacity Lithium-Metal Battery.

The realization of lithium-metal (Li) batteries faces challenges due to dendritic Li deposition causing internal short-circuit and low Coulombic efficiency. In this regard, the Li-deposition stability largely depends on the electrolyte, which reacts with Li to form a solid electrolyte interphase (SEI) with diverse physico-chemical properties, and dictates the interphasial kinetics. Therefore, optimizing the electrolyte for stability and performance remains pivotal. Hereof, glyme ethers are an emerging class of electrolytes, showing improved compatibility with metallic Li and enhanced stability in Li─Air and Li─Sulfur batteries. Yet, the criteria for selecting glyme solvents, particularly concerning Li deposition and dissolution processes, remain unclear. The SEI characteristics and Li deposition/dissolution processes are investigated in glyme-ether-based electrolytes with varying chain lengths, using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO₃) salts under high capacity and limited electrolyte conditions. Longer glymes led to more homogeneous SEI, particularly pronounced with LiNO₃, minimizing surface roughness during stripping, and promoting compact Li deposits. Higher reductive stability, resulting in homogeneous interphasial properties, and slower kinetics due to high desolvation barrier and viscosity, underline stable Li growth in longer glymes. This study clarifies factors guiding the selection of glyme ether-based electrolytes in Li metal batteries, offering insights for next-generation energy storage systems.