High ionic conductivity of new polymer electrolytes consisting of polypyridinium, pyridinium and aluminium chloride

Watanabe, Masayoshi; Yamada, Shusaku; Sanui, Kohei; Ogata, Naoya

doi:10.1039/c39930000929

Cited by 82 publications

(52 citation statements)

References 7 publications

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“…The class of PEs obtained by this method are termed "polymer-in-salt" electrolytes [10], and were independently reported by Angell [11] and one of the authors of this paper [12] in 1993 for the first time. We proposed the use of polymer electrolytes consisting of polymers and ionic liquids (ILs), which are molten salts with melting points lower than 100 C [13][14][15].…”

Section: Introductionmentioning

confidence: 90%

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Kido

Ueno

Iwata

et al. 2015

Electrochimica Acta

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Keywords: solvate ionic liquid polymer electrolyte polymer-in-salt ionicity glyme A B S T R A C T Polymer electrolytes (PEs) have served as the focus of intensive research as new ion-conducting materials, especially for lithium battery applications. A new strategy to develop fast lithium-conducting PEs is reported here. The thermal, ionic transport, and electrochemical properties of polymer solutions in a glyme-Li salt solvate ionic liquid, [Li(G4) 1 ][TFSA], composed of an equimolar mixture of lithium bis (trifluoromethanesulfonyl) amide (Li[TFSA]) and tetraglyme (G4), were characterized. Poly(ethylene oxide) (PEO), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were combined with [Li(G4) 1 ][TFSA] in order to explore the effects of polymer structure on the properties. The self-diffusion coefficient ratio of the glyme and Li + ions (D G /D Li ) was investigated to evaluate the stability of the complex (solvate) cations. The D G /D Li values suggested that the [Li(G4) 1 ] + complex cations underwent a ligand exchange reaction between G4 and PEO in the PEO-based solution, whereas the cations remained stable (D G /D Li = 1) in the PMMA-and PBA-based solutions. The robustness of the [Li(G4) 1 ] + complex cations in the PMMA-and PBA-based solutions was reflected in high weight-loss temperature, greater Li transference number, and high oxidative stability.Owing to the lower glass transition temperature and low affinity towards Li + ions, the PBA-based solutions yielded superior lithium transport properties (ionic conductivity of 10 À4 $10 À3 Scm À1 and Li transference number as high as 0.5) among the investigated polymer solutions.

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Section: Introductionmentioning

confidence: 90%

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Kido

Ueno

Iwata

et al. 2015

Electrochimica Acta

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“…10 In 1993, the current authors published the first report on a polymer electrolyte having an exceptionally high ionic conductivity at that time, which was a molecular composite consisting of a chloroaluminate IL and a polymer. 11 To the best of our knowledge, this was the first report on the materialization of an IL/synthetic-polymer combination. Subsequently, we found that common vinyl monomers are widely soluble in common ILs and that they can be polymerized in ILs by freeradical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Polymers in Ionic Liquids: Dawn of Neoteric Solvents and Innovative Materials

Ueki

Watanabe

2011

Bulletin of the Chemical Society of Japan

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154

144

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In this paper, we review recent advances in the use of polymers in ionic liquids (ILs) from the view point of the "dawn of neoteric solvents and innovative materials." The first part of this paper presents a brief review of the solubility parameters of ILs, which are expected to serve as a qualitative guide for predicting polymer solubility in ILs; however, this concept cannot be used to rationalize a number of cases in which strong Coulombic interactions dominate the solubility parameters of the ILs. Thus, solubility of 24 different common synthetic polymers is experimentally demonstrated under dilute conditions (3 wt %) in four different common ILs. It is found that the Lewis basicities of the counter anions in the ILs play an important role in determining the solubility of the polymers. ILs can also be used as good solvents for low-solubility biopolymers and as good dispersion media of carbon nanotubes, which contributes to the fields of biorefinery processes and advanced materials. Certain combinations of polymers in ILs undergo phase separations as the temperature of the solutions is varied. The solubility of a nonionic polymer in water generally decreases with increasing temperature, and certain combinations exhibit lower critical solution temperature (LCST) phase separation, whereas the solubility of a polymer in an organic solvent generally increases with increasing temperature and in some cases upper critical solution temperature (UCST) phase separation is observed. Interestingly, both LCST and UCST phase separations are observed for certain polymers in ILs. After presenting possible explanations of the solubility of polymers in ILs, recent developments in the field of thermosensitive polymers in ILs are discussed from the perspective of materials science, where such phase separations are exploited to trigger abrupt changes in polymer properties. The final part of this review describes the thermosensitive self-assembly of block copolymers in ILs. Similar to conventional molecular solvents, block copolymers in ILs exhibit variable self-assemblies in solution and in the bulk.

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“…Polymer electrolytes 1 have occupied an important position in solid-state ionics because of their unique properties, such as film-forming capabilities, good processibility, flexibility, light weight, elasticity (plasticity), transparency, a relatively high ionic conductivity, and a wide potential window. Some of these characteristics cannot be attained by hard inorganic solid electrolytes, including inorganic glasses, and thus, polymer electrolytes have been exploited to bridge a gap between fluid electrolyte solutions and hard inorganic solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of quaternized poly(4‐vinylpyridine‐co‐styrene) membranes

Huang

Xiao

Zhuang

2005

J of Applied Polymer Sci

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Copolymers of 4-vinylpyridine and styrene [P(4VP-St)s] with varied molar ratios were synthesized by means of radical mass polymerization with 2,2Ј-azobisisobutyronitrile as an initiator. The insoluble (linear) pyridinium-type polymers in the octyl-pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP-St) with 1-bromooctane. A series of membranes were prepared for use in electrochemistry. These membranes, prepared with quaternized poly(styrene-co-4-vinylpyridine), were characterized by IRspectroscopy, Xray diffraction, differential scanning calorimetry, thermogravimetory, tensile strength measurements, scanning electron microscopy, and an electrochemistry workstation. Our emphasis was to select a membrane with appropriate properties for use in the electrochemistry field. A promising membrane was selected to use in the field of electrochemistry by these characterizations. This study could be the preparation for a study on the electrochemical properties of pyridinium-type polymers.

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High ionic conductivity of new polymer electrolytes consisting of polypyridinium, pyridinium and aluminium chloride

Cited by 82 publications

References 7 publications

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Li+ Ion Transport in Polymer Electrolytes Based on a Glyme-Li Salt Solvate Ionic Liquid

Polymers in Ionic Liquids: Dawn of Neoteric Solvents and Innovative Materials

Synthesis and characterization of quaternized poly(4‐vinylpyridine‐co‐styrene) membranes

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