Highly Conductive Polymer Electrolytes Constructed from Polymerizable Ionic-Liquid and Inorganic Cluster

Abstract

Conductive inorganic-organic hybrid monomers and polymers were successfully obtained by using a polymerizable imidazolium ionic-liquid with a methacryloyl group (denoted as MAImC 1) and inorganic polyoxometalate cluster anion ([SiW 12 O 40 ] 4− , SiW 12). The MAImC 1-SiW 12 hybrid monomer was synthesized as single crystals, the molecular and crystal structures of which were revealed by single crystal X-ray analysis. The obtained MAImC 1-SiW 12 hybrid monomer was found to be polymerized by a radical polymerization using AIBN as an initiator to form inorganic-organic homo-and copolymers. The hybrid copolymers of MAImC 1-SiW 12 polymerized with another polymerizable ionic-liquid (denoted as MAImC 8) exhibited high conductivity of 10 −3 S cm −1 order under humidified condition at near room temperature of 313 K.

Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids

“…The POM anions hybridized were β-type octamolybdate ([Mo 8 O 26 ] 4– (Mo 8 ), Figure 1b) and dodecatungstosilicate ([SiW 12 O 40 ] 4– (SiW 12 ), Figure 1b), both of which are anions with a 4− charge. Hybrid crystals with Mo 8 and SiW 12 have been reported previously [42,44]. The hybrid crystals with MAImC 8 contained anisotropic arrangements of POM anions in their bulk crystal structures due to the presence of an amphiphilic moiety, while hybrid crystals with MAIm exhibited isotropic POM arrangements.…”

“…70% yield for MAImC 8 –SiW 12 ( 4 ), respectively. The characteristic peaks of SiW 12 [17,44,55] were observed for as-prepared 3 (Figure 5a) and 4 (Figure 5c) in the range of 400–1100 cm −1 of IR spectra. The presence of the polymerizable ionic liquids were confirmed by the IR spectra (in the range of 2800–3000 cm −1 for methylene groups and 1200–1800 cm −1 for methacryloyl group), which showed successful formation of the hybrid crystals comprising SiW 12 and the polymerizable ionic liquids.…”

“…These hybrid crystals contained four polymerizable ionic liquid cations (1+ charge) associated with one SiW 12 anion (4− charge). All of the protons of the starting H–SiW 12 were replaced by ion-exchange reactions without remaining counter cations after the hybridization [44,56,57,58], which was different from the cases of Mo 8 hybrid crystals of 1 and 2 . Both recrystallized SiW 12 hybrid crystals of 3 and 4 contained the solvents of crystallization (1,4-dioxane utilized in the recrystallization process for 3 ; 1,4-dioxane and water for 4 ), which also contrasts with the Mo 8 hybrid crystals of 1 and 2 .…”

“…All chemical reagents were purchased from FUJIFILM Wako Pure Chemical Corporation (Osaka, Japan) and Tokyo Chemical Industry Co., Ltd. (TCI, Tokyo, Japan). The starting polymerizable ionic liquid of [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 ] (denoted as MAIm–N) was synthesized as a neutral compound, and [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 (C 8 H 17 )]Br (MAImC 8 ·Br) were synthesized as bromide salts according to previous studies (Figure S1) [42,43,44].…”

“…Recently, we designed a polymerizable ionic liquid cation with an imidazolium moiety with a methacryloyl group ([{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 (CH 3 )] + , denoted as MAImC 1 , Figure 1a), and successfully synthesized inorganic–organic hybrid monomers and polymers with several POM anions [42,43,44]. These MAImC 1 –POM hybrids were isolated as single crystals with clarified structures, and behaved as monomers of hybrid polymers exhibiting high conductivity as solid electrolytes [44]. In the MAImC 1 –POM hybrid monomers, the POM arrangements in the bulk crystal structures were isotropic due to the small molecular size of the MAImC 1 cation.…”