Effects of repeat unit charge density on the physical and electrochemical properties of novel heterocationic poly(ionic liquid)s

Cotessat, Merlin; Flachard, Dimitri; Nosov, Daniil R.; Lozinskaya, Elena I.; Ponkratov, Denis O.; Schmidt, Daniel F.; Drockenmuller, Éric; Shaplov, Alexander S.

doi:10.1039/d0nj04143b

Cited by 12 publications

(9 citation statements)

References 63 publications

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“…The ionic conductivity of the PDM-TFSI-2-based electrolyte is higher than that of the PDM-TFSI-1-based electrolyte; this may be determined by two aspects: one is the charge density of each monomer unit, and the other is the number of groups around the monomer that can dissolve ions. 45 So, this phenomenon might be derived from the six-substituted benzene ion network: each benzene ring has a higher charge density; on the one hand due to the steric hindrance effect between TFSI anions and on the other hand due to the solvation effect of the ionic liquid on the TFSI anion, TFSI is easier to leave. In addition, the symmetric Li/ PDM-TFSI-1@LiTFSI-DEMETFSI/Li and Li/PDM-TFSI-2@LiTFSI-DEMETFSI/Li cells were assembled to determine the Li + transference number (t Li+ ) using electrochemical impedance spectroscopy and chronoamperometry.…”

Section: Resultsmentioning

confidence: 99%

“…Ionic conductivity and lithium ion transfer number are two important factors of solid electrolytes. The ionic conductivity of the PDM-TFSI-2-based electrolyte is higher than that of the PDM-TFSI-1-based electrolyte; this may be determined by two aspects: one is the charge density of each monomer unit, and the other is the number of groups around the monomer that can dissolve ions . So, this phenomenon might be derived from the six-substituted benzene ion network: each benzene ring has a higher charge density; on the one hand due to the steric hindrance effect between TFSI anions and on the other hand due to the solvation effect of the ionic liquid on the TFSI anion, TFSI is easier to leave.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Fortunately, recent studies have shown that ionic conductivity is related not only to the number of charges per monomer but also to the number of ions that can be dissolved around it. 45 Even with some progress, the conductivity of PILs is still lower than that of the lithium battery commercial liquid electrolyte (around 10 −2 S cm −1 at 25 °C, 1.0 M LiPF 6 in EC:DEC:EMC = 1:1:1 vol %). 46 Based on these findings, we were inspired to design a class of polymer networks with high charge density, ionic liquids that solvate the charge carriers in the ion network and therefore provide a satisfactory ionic conductivity.…”

Section: Introductionmentioning

confidence: 99%

“…For example, from the perspective of charge density alone, the ionic conductivity of the same 1,2,3-triazolium-based polyionic compound possessing a larger charge density (>10 –8 S cm –1 at 30 °C) is, on the contrary, lower than that of the polyionic liquid possessing a lower charge density (7 × 10 –5 S cm –1 at 30 °C). , In contrast to the above example, the ionic conductivity of an electrolyte with a monomer having a double cation (4.6 × 10 –5 S cm –1 at 25 °C) is an order of magnitude higher than that of an electrolyte with a monomer having only one cation (≈10 –6 S cm –1 at 25 °C). , Therefore, many factors should be considered when designing materials with high ionic conductivity. Fortunately, recent studies have shown that ionic conductivity is related not only to the number of charges per monomer but also to the number of ions that can be dissolved around it . Even with some progress, the conductivity of PILs is still lower than that of the lithium battery commercial liquid electrolyte (around 10 –2 S cm –1 at 25 °C, 1.0 M LiPF 6 in EC:DEC:EMC = 1:1:1 vol %) .…”

Section: Introductionmentioning

confidence: 99%

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Polymerized Ionic Networks Solid Electrolyte with High Ionic Conductivity for Lithium Batteries

Guo

Liu

Wei

et al. 2021

Ind. Eng. Chem. Res.

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The performance of classical lithium-ion technologies based on liquid electrolytes has made great advances in the last two decades, but safety issues are inevitable for batteries assembled with liquid electrolytes, which have intrinsic instability. In response to this issue, solid polymer electrolytes are developed in the lithium batteries field extensively for improving safety issues, as well as miniaturizing and enhancing the energy densities. Considering the great advantages of polymerized ionic networks, such as facile synthesis, high charge density, and high stability, two polymerized ionic networks (PDM-TFSI-1 and PDM-TFSI-2) with different polysubstituted benzene groups have been developed. The new type of polymerized ionic network with cross-linked structure was synthesized by the simple radical copolymerization of 2-(dimethylamino)ethyl methacrylate and methyl methacrylate monomers, then the copolymer (M n = 14.5 kg mol−1) reacted with polysubstituted bromobenzene to form a cross-linked structure, and finally this was ion exchanged with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). The ionic networks filled with ionic liquid/LiTFSI mixture exhibit high ionic conductivity (1.0 × 10–4 and 1.9 × 10–4 S cm–1) and high decomposition potential (4.7 V vs Li/Li+) at 30 °C. The batteries were assembled by sandwiching the obtained polymer electrolytes between a LiFePO4 cathode and a lithium anode, exhibiting good cycling stability and specific capacity, suggesting that these novel kinds of solid polymer electrolyte are promising for application in next-generation lithium-ion batteries.

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Section: Resultsmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Polymerized Ionic Networks Solid Electrolyte with High Ionic Conductivity for Lithium Batteries

Guo

Liu

Wei

et al. 2021

Ind. Eng. Chem. Res.

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“…This result strongly suggests that T g plays a dominant role in ion transport in both monocationic and dicationic TPILs, especially with charge placement in the polymer backbone. 36,37 Based on these results, we concluded that the introduction of a long ethylene oxide spacer or an increase in the IL moiety in the monomer unit contributes to a decreasing T g value for the resultant TPILs, which results in enhanced polymer chain relaxation, and ultimately, a higher ionic conductivity.…”

Section: Ion Conductingmentioning

confidence: 89%

Design of Clickable Ionic Liquid Monomers to Enhance Ionic Conductivity for Main-Chain 1,2,3-Triazolium-Based Poly(Ionic Liquid)s

2021

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A series of clickable α-azide-ω-alkyne ionic liquid (IL) monomers with an ethylene oxide spacer were developed and applied to the synthesis of 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) with high ionic conductivities via one-step thermal azide–alkyne cycloaddition click chemistry. Subsequently, the number of IL moieties in the resultant TPILs was further increased by N -alkylation of the 1,2,3-triazole-based backbones of the TPILs with a quarternizing reagent. This strategy affords the preparation of TPILs having either one or two 1,2,3-triazolium cations with bis(trifluoromethylsulfonyl)imide anions in a monomer unit. Synthesis of the TPILs was confirmed by 1 H and 13 C NMR spectroscopy and gel permeation chromatography. The effects of the length of the ethylene oxide spacer and the number of IL moieties in the IL monomer unit on the physicochemical properties of the TPILs were characterized by differential scanning calorimetry, thermogravimetric analysis, and impedance spectroscopy. The introduction of a longer ethylene oxide spacer or an increase in the number of IL moieties in the monomer unit resulted in TPILs with lower glass-transition temperatures and higher ionic conductivities. The highest ionic conductivity achieved in this study was 2.0 × 10 –5 S cm –1 at 30 °C. These results suggest that the design of the IL monomer provides the resultant polymer with high chain flexibility and a high IL density, and so it is effective for preparing TPILs with high ionic conductivities.

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1,3,4,5‐Tetrasubstituted Poly(1,2,3‐triazolium) Obtained through Metal‐Free AA+BB Polyaddition of a Diazide and an Activated Internal Dialkyne

Akacha,

Abdelhedi‐Miladi,

Serghei

et al. 2024

Macromol. Rapid Commun.

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A tetra(ethylene glycol)‐based 1,3,4,5‐tetrasubstituted poly(1,2,3‐triazolium) is synthesized in two steps including: i) the catalyst‐free polyaddition of a diazide and an activated internal dialkyne and ii) the N‐alkylation of the resulting 1,2,3‐triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3‐triazole)s are obtained via AA+BB polyaddition using copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) or metal‐free thermal alkyne‐azide cycloaddition (TAAC). Poly(1,2,3‐triazole)s with higher molar masses are obtained in higher yields by TAAC polyaddition. A 1,3,4‐trisubstituted poly(1,2,3‐triazolium) structural analog obtained by TAAC polyaddition using a terminal activated dialkyne and subsequent N‐alkylation of the 1,2,3‐triazole groups enables discussing the influence of the methyl group in the C‐4 or C‐5 position on thermal and ion conducting properties. Obtained polymers are characterized by 1H, 13C, and 19F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography and broadband dielectric spectroscopy. The targeted 1,3,4,5‐tetrasubstituted poly(1,2,3‐triazolium) exhibits a glass transition temperature of −23 °C and a direct current ionic conductivity of 2.0 × 10−6 S cm−1 at 30 °C under anhydrous conditions. The developed strategy offers opportunities to further tune the electron delocalization of the 1,2,3‐triazolium cation and the properties of poly(1,2,3‐triazolium)s using this additional substituent as structural handle.This article is protected by copyright. All rights reserved

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Effects of repeat unit charge density on the physical and electrochemical properties of novel heterocationic poly(ionic liquid)s

Abstract: The higher the charge density of PILs the higher their Tg and the lower their conductivity; the best conductivity (1.8 × 10−5 S cm−1 at 25 °C): PILs with triazolium cations; the best cathodic stability (−0.4 V vs. Li+/Li at 70 °C): PILs with mixed type cations.

Cited by 12 publications

References 63 publications

Polymerized Ionic Networks Solid Electrolyte with High Ionic Conductivity for Lithium Batteries

Polymerized Ionic Networks Solid Electrolyte with High Ionic Conductivity for Lithium Batteries

Design of Clickable Ionic Liquid Monomers to Enhance Ionic Conductivity for Main-Chain 1,2,3-Triazolium-Based Poly(Ionic Liquid)s

1,3,4,5‐Tetrasubstituted Poly(1,2,3‐triazolium) Obtained through Metal‐Free AA+BB Polyaddition of a Diazide and an Activated Internal Dialkyne

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