Thermochemistry of hydrogen bonding of ethers with aliphatic alcohols

Rakipov, Ilnaz T.; Semenov, Konstantin N.; Petrov, Аrtem А.; Akhmadiyarov, Aydar A.; Khachatrian, Artashes A.; Gainutdinova, Aliya Z.; Varfolomeev, Mikhail A.

doi:10.1016/j.tca.2022.179203

“…The Raman and FT-IR spectra indicate that the FEC-ES interaction is much weaker than the ES-ES and FEC-ES interaction, consistent with the above theoretical calculation. [18] Further, nuclear overhauser effect spectroscopy (NOESY) in Figure 2f and Figure S3 indicates weak intermolecular interactions of ES and FEC due to no new peaks emerging compared to the pure solvent.…”

Section: Weakening Of Intermolecular Interactionmentioning

confidence: 95%

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

Wang,

Li,

Xie

et al. 2024

Angew Chem Int Ed

6

0

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Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium‐based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi0.8Mn0.1Co0.1O2||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah−1, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.

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“…It is well accepted that the protonated cation acted as a hydrogen bonding donor and the corresponding organic carboxylic acid anion acted as a hydrogen bonding acceptor in the protic ILs, thus endowing its solubility to natural polymers. Previous research has indicated that the ether structure has a unique ability to establish hydrogen bonds with other molecules (e.g., water, alcohols, acids, and amines) due to the presence of oxygen atoms. , Therefore, it can be envisioned that the introduction of an ether structure moiety into the organic carboxylic acid anion in protic ILs can strengthen its hydrogen bonding acceptor sites, thus resulting in desirable solubility to cellulose and SF. Hence, in this study, methoxyacetic acid (Mea), with an ether structure moiety, and several organic superbases with different basicities were used to prepare several ether-functionalized protic ILs, and the solubility of SF and the simultaneous dissolution of silk fibroin and cellulose was studied systematically, and the rheological properties of SF/cellulose solutions were conducted, on which, a series of SF/cellulose composite fibers were also prepared by wet spinning, and the effect of draft ratio on the structure and properties of composite fibers was systematically investigated.…”

Section: Introductionmentioning

confidence: 99%

Molecularly Engineer Protic Ionic Liquids for Simultaneous Dissolution of Silk Fibroin/Cellulose and Wet-Spinning Composite Fibers Preparation through Hydrogen-Bonding-Acceptor-Strengthening Strategy

Chen,

Zhang,

Guo

et al. 2024

ACS Sustainable Chem. Eng.

3

0

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With over 20 years of continued development of ionic liquids (ILs) for natural polymer processing and conversion, the design and facile preparation of ILs is still a hot research topic. In this study, a hydrogen bonding acceptor strengthening strategy was applied to design ether functionalized protic ILs, which were synthesized by a solvent-free neutralization reaction of methoxyacetic acid (Mea) and 1,5-diazabicyclo [4.3.0]-5-nonene (DBN). The ether-functionalized protic ILs ([DBNH][Mea]) were identified as a satisfactory solvent for the simultaneous dissolution of silk fibroin (SF) and cellulose at mild conditions, thus delivering a new dissolution processing platform toward value-added SF-based regenerated fiber materials. The strengthened simultaneous dissolution mechanism of SF and cellulose in [DBNH][Mea] by the introduction of an ether structure moiety in the anion was experimentally and computationally verified, and the results indicated that the ether structure moiety endowed it with more hydrogen-bonding acceptor sites, thus presenting stronger hydrogen-bonding disruption ability and outstanding solubility to SF and cellulose under mild conditions. Rheological study of the SF/cellulose/[DBNH][Mea]/DMSO solutions was conducted systematically, and the correlations between apparent viscosity (η), activation energy (Εη), overlap concentration (c*), structural viscosity index (Δη), storage modulus (G′) and loss modulus (G′′) of the solutions were highly correlated to the mass ratio of SF to cellulose. A series of SF/cellulose composite fibers were prepared by wet spinning using ethanol as the coagulation bath, and the obtained composite fibers were analyzed by Fourier transform infrared (FTIR), X-ray diffraction (XRD), elemental analysis, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) and mechanical tests. It was found that the composite fibers had high compatibility and the postdrafting technique is beneficial for enhancing the mechanical robustness.

show abstract

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

Wang,

Li,

Xie

et al. 2024

View full text Add to dashboard Cite

Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium‐based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi0.8Mn0.1Co0.1O2||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah−1, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.

show abstract

Thermochemistry of hydrogen bonding of ethers with aliphatic alcohols

Cited by 6 publications

References 22 publications

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

Molecularly Engineer Protic Ionic Liquids for Simultaneous Dissolution of Silk Fibroin/Cellulose and Wet-Spinning Composite Fibers Preparation through Hydrogen-Bonding-Acceptor-Strengthening Strategy

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

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