Improved ionic conductivity for amide-containing electrolytes by tuning intermolecular interaction: the effect of branched side-chains with cyanoethoxy groups

Yamada, Koki; Yuasa, Shohei; Matsuoka, Riho; Sai, Ryansu; Katayama, Yu; Tsutsumi, Hiromori

doi:10.1039/d1cp00852h

Cited by 11 publications

(5 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To enhance the ion activity in the electrolyte, we employed BMI-Br, an OIPC type, and expected an amide and bromine interaction with PEO. [46,47] Lithium salt and BMI-Br solid plasticizer were added to the PEO matrix, and the CPE was obtained through drying. The moisture sensitivity of BMI-Br required conducting all procedures in a glove box.…”

Section: Resultsmentioning

confidence: 99%

Functionality of 1‐Butyl‐2,3‐Dimethylimidazolium Bromide (BMI‐Br) as a Solid Plasticizer in PEO‐Based Polymer Electrolyte for Highly Reliable Lithium Metal Batteries

Kim,

Jamal,

Jeon

et al. 2023

Advanced Energy Materials

View full text Add to dashboard Cite

To address the challenges associated with solid polymer electrolytes, flame‐retardant organic ionic plastic crystals (OIPCs) have been utilized as a solid plasticizer in composite polymer electrolytes (CPEs). In this study, 1‐butyl‐2,3‐dimethylimidazolium bromide (BMI‐Br) is used as an OIPC material. BMI‐Br and LiTFSI are initially mixed in an acetonitrile (ACN) organic solvent for a certain time. Anion exchange takes place in this mixing, replacing the Br− in BMI‐Br with TFSI−. As a result, BMI‐TFSI and Li‐Br are formed. Here, BMI‐TFSI acts as an ionic liquid, while Li‐Br serves as a salt. The 10% BMI‐Br content (BMI‐Br‐10 CPE) exhibits significant ionic conductivity (σ = 2.34 × 10−3 S cm−1 at 30 °C), wide window (up to 4.57 V), and flame retardancy. Furthermore, the BMI‐Br‐10 CPE demonstrates galvanostatic lithium plating stripping cycling stability at 100 and 300 µA cm−2 for 800 and 500 h against Li‐metal, respectively, without a significant overpotential shooting. Furthermore, at 60 °C, the BMI‐Br‐10 CPE in [LiFePO4/BMI‐Br‐10/Li] batteries demonstrates an initial capacity of 146.9 mAh g−1, capacity retention of 99.7% and high coulombic efficiency (99.5%) after 300 cycles at 1C.

show abstract

Section: Resultsmentioning

confidence: 99%

Functionality of 1‐Butyl‐2,3‐Dimethylimidazolium Bromide (BMI‐Br) as a Solid Plasticizer in PEO‐Based Polymer Electrolyte for Highly Reliable Lithium Metal Batteries

Kim,

Jamal,

Jeon

et al. 2023

Advanced Energy Materials

View full text Add to dashboard Cite

show abstract

“…At the same time, the band belonging to C═O shows a blue shift from 1725 to 1717 cm −1 , and a new band at 3305 cm −1 appears, which can be attributed to the formation of -NH-. [28] The blue shift of carbonyl group and the simultaneous occurrence of the amino group may indicate the formation of amide bonds. [13c,29] X-ray photoelectron spectroscopy (XPS) was further used to characterize PMHA and c-PMHA.…”

Section: Characterizing Pmha and C-pmhamentioning

confidence: 99%

In Situ Forming Gel Polymer Electrolyte for High Energy‐Density Lithium Metal Batteries

Xue,

Liu,

Xiang

et al. 2023

Small

View full text Add to dashboard Cite

In situ forming gel polymer electrolyte (GPE) is one of the most feasible ways to improve the safety and cycle performances of lithium metal batteries with high energy density. However, most of the in situ formed GPEs are not compatible with high‐voltage cathode materials. Here, this work provides a novel strategy to in situ form GPE based on the mechanism of Ritter reaction. The Ritter reaction in liquid electrolyte has the advantage of appropriate reaction temperature and no additional additives. The polymer chains are cross‐linked by amide groups with the formation of GPE with superior electrochemical properties. The GPE has high ionic conductivity (1.84 mS cm−1), wide electrochemical stability window (>5.25 V) and high lithium ion transference number (≈0.78), compatible with high‐voltage cathode materials. The Li|LiNi0.6Co0.2Mn0.2O2 batteries with in situ formed GPE show excellent long‐term cycle stability (93.4%, 300 cycles). The density functional theory calculation and X‐ray photoelectron spectroscopy results verify that the amide and nitrile groups are beneficial for stabilizing cathode structure and promoting uniform Li deposition on Li anode. Furthermore, the in situ formed GPE exhibits excellent electrochemical performance in Graphite|LiMn2O4 and Graphite|LiNi0.5Co0.2Mn0.3O2 pouch batteries. This approach is adaptable to current battery technologies, which will be sure to promote the development of high energy‐density lithium‐ion batteries.

show abstract

“…The photophysical phenomena and conductivity of polymers are influenced at large by conventional and nonconventional hydrogen bonds; electrostatic interactions; and through-bond/-space conjugation-assisted supramolecular interactions; aggregation; solvent polarity; branching of heteroatomic nontraditional luminophores (NTLs); band gap; and oxidation–reduction. − In this context, both ex situ-added and in situ-anchored monomers along with the functionalities of their pendent side chains play significant roles in determining the supramolecular interaction-associated photophysical properties, chemosensing, and conductivity of nonconjugated polymers. Notably, secondary amidic N -(monomethylol)acrylamide (MMA) has been chosen as one of the comonomers of FCP s, as MMA imparts rigidity, stiffness, and steric hindrance by N -branching; hydrophilicity; and hydrogen-bonding-associated interactions of primary alcohol (−CH 2 OH) and secondary amide (−CONH) groups to enlarge the fluorescence efficacy. − Interestingly, the rotation around the amidic C–N bond is expected to be restricted by resonance along with the electron delocalization index between nitrogen and oxygen atoms in amides, leading to the proton transfer and amide–imidol (−CONH/–CN(OH)) tautomerism . Thus, in FCP s, RIR can promote the dual light emission through excited-state intramolecular proton transfer (ESIPT) leading to the conversion of amide to imidol .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Intrinsically Dual-Emissive Aliphatic Conducting Polymer and ESIPT-Associated Switching of Amide-Aggregate to Imidol-Aggregate for Sensing of Cr(III) and Fe(III)

Mitra,

Sanfui,

Roy

et al. 2023

Macromolecules

View full text Add to dashboard Cite

The design, synthesis, and optimization of excited-state intramolecular proton transfer (ESIPT)-associated dual-emissive aliphatic conductive polymer is one of the very challenging tasks, and has not been reported to date. Herein, aliphatic fluorescent conducting polymers (FCPs) are synthesized by polymerizing N-(monomethylol)acrylamide (MMA), acrylic acid (AA), and in situ-generated 3-N-(monomethylolacrylamido)propanoic acid (NMMAPA). Of different FCPs, the maximum population of heteroatomic nontraditional luminophores, i.e., secondary amide (−CONH), imidol (−CN(OH)), tertiary amide (−CON), and carboxylic acid (−COOH), in FCP4 is supported by the spectroscopic analyses, thermal profiles, fluorescence enhancements, and computational calculations. Thus, further investigations are made on FCP4 to explore the photophysical properties, check the suitability in dual metal ion sensing, and study the proton conductivity. The ESIPT-associated dual light emissions at 436 nm (λem1) and 573/617 nm (λem2) originate from FCP4 (amide)/FCP4 (amide)-aggregate and FCP4 (imidol)/FCP4 (imidol)-aggregate, respectively, and are supported by concentration-dependent emissions, time-correlated single photon counting studies, solvent polarity effects, and computational measurements. Regarding this, the high fluorescence quantum yields of 0.68 and 0.18 at λem1 and λem2, respectively, confirmed the ESIPT-associated strong dual emissions of FCP4. The UV spectrum within 264–300 nm, FTIR peak at 2165 cm–1, binding energies of −CN(OH)/–CN(OH) at 399.0/533.4 eV, and computational studies indicate the coexistence of FCP4 (amide)/FCP4 (amide)-aggregate and FCP4 (imidol)/FCP4 (imidol)-aggregate forms of FCP4. In FCP4, −CONH/–CN(OH)/–CON/–COOH/–CH2OH-associated dipolar and hydrogen-bonding interactions, n−π* transitions, and N-branching-associated rigidity contribute to ESIPT-associated amide–imidol phototautomerism, aggregation-enhanced emissions, dual light emissions, metal ion sensing, and conductivity. The strong coordinations of Fe(III) and Cr(III) with FCP4 (amide) and FCP4 (imidol), respectively, are supported by spectroscopic, thermal, and computational studies. The strong quenching efficiencies of Fe(III) and Cr(III) are indicated by the very low limits of detection of 0.1142 and 0.0534 ppb, respectively. The I–V and ac impedance spectroscopy data of FCP4 having 0.28 cm thickness and 1.72 cm2 area indicate high proton conductivities of 3.53 × 10–5 and 3.22 × 10–5 S cm–1 at pH = 7.0 and 8.0, respectively.

show abstract

Improved ionic conductivity for amide-containing electrolytes by tuning intermolecular interaction: the effect of branched side-chains with cyanoethoxy groups

Abstract: Polymeric materials are considered as promising electrolytes for all-solid-state secondary lithium batteries with superior energy and power densities, long cycle lives, and safety. To further improve the ionic conductivity of...

Cited by 11 publications

References 57 publications

Functionality of 1‐Butyl‐2,3‐Dimethylimidazolium Bromide (BMI‐Br) as a Solid Plasticizer in PEO‐Based Polymer Electrolyte for Highly Reliable Lithium Metal Batteries

Functionality of 1‐Butyl‐2,3‐Dimethylimidazolium Bromide (BMI‐Br) as a Solid Plasticizer in PEO‐Based Polymer Electrolyte for Highly Reliable Lithium Metal Batteries

In Situ Forming Gel Polymer Electrolyte for High Energy‐Density Lithium Metal Batteries

Synthesis of Intrinsically Dual-Emissive Aliphatic Conducting Polymer and ESIPT-Associated Switching of Amide-Aggregate to Imidol-Aggregate for Sensing of Cr(III) and Fe(III)

Contact Info

Product

Resources

About