Ito Takeru, Otobe Saki, Oda Tatsuma, Kojima Tatsuhiro, Ono Seiji, Watanabe Masayuki, Kiyota Yoshiki, Misawa Toshiyuki, Koguchi Shinichi, Higuchi Masashi, Kawano Masaki, Nagase Yu
Department of Chemistry, School of Science, Tokai University, 4-1-1 Kitakaname, Hiratsuka 259-1292, Japan.
Department of Applied Chemistry, School of Engineering, Tokai University, Hiratsuka, Kanagawa 259-1292, Japan.
Polymers (Basel). 2017 Jul 20;9(7):290. doi: 10.3390/polym9070290.
Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC₁), were successfully hybridized with heteropolyanions of [PWO] (PW) to form inorganic-organic hybrid monomers of MAImC₁-PW. The synthetic procedure of MAImC₁-PW was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC₁-PW was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC₁-PW was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10 S·cm order under humidified conditions at 313 K.
固态电解质因其结构稳定性和易于处理而成为锂离子或燃料电池技术的关键材料。固态电解质中高电导率的出现需要精确控制其组成和结构。一种制备高导电固态电解质的有效策略是采用热稳定的无机组分和结构灵活的有机部分来构建无机-有机杂化材料。离子液体作为有机组分有利于高电导率的出现，而多金属氧酸盐，如杂多酸，是众所周知的无机质子导体。在此，新设计的具有可聚合甲基丙烯酸基团的咪唑鎓阳离子（表示为MAImC₁）成功地与[PWO]（PW）的杂多阴离子杂交，形成了MAImC₁-PW无机-有机杂化单体。MAImC₁-PW的合成过程是一个简单的离子交换反应，原则上通常适用于几种多金属氧酸盐。MAImC₁-PW以单晶形式获得，其分子和晶体结构得到了清晰的揭示。此外，MAImC₁-PW杂化单体以偶氮二异丁腈为引发剂通过自由基聚合进行聚合。在313K的潮湿条件下，一些所得的无机-有机杂化聚合物表现出10 S·cm级别的电导率。
