Preparation of ion conductive inorganic-organic composite systems by in situ sol-gel reaction of polymerizable ionic liquids
Preparation of ion conductive inorganic-organic composite systems by in situ sol-gel reaction of polymerizable ionic liquids
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DOI：
10.1002/pat.1221
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发表时间：
2008-10-01
影响因子：
3.4
通讯作者：
Ohno, Hiroyuki
中科院分区：
文献类型：
--
作者：
Mizumo, Tomonobu;Watanabe, Takeshi;Ohno, Hiroyuki
采用可聚合离子液体和功能性硅酸盐或硼硅酸盐网络，通过原位溶胶凝胶加工制备了传导锂离子的无机-有机复合材料。在锂盐存在下，1-乙基-3-乙烯基咪唑鎓双（三氟甲磺酰基）酰亚胺（[evim][Tf2N]）的自由基聚合与四甲氧基硅烷（TMOS）与各种三烷氧基硼烷（例如三甲氧基硼烷（TMOB）、三异丙氧基硼烷（TiPOB）或异丙基二甲氧基硼烷 (Mes-DMOB)。许多所得复合材料以透明或半透明玻璃状固体形式获得。由于无机网络和聚合离子液体的高热稳定性，该复合材料具有高于 300 摄氏度的高分解温度。通过增加有机化合物的比例来增加离子电导率。添加LiTf2N也改变了化合物的离子电导率，至少达到10(-5)；室温下 S cm(-1)。 LiSO3CF3 掺杂体系的离子电导率比该值低约一个数量级。发现离子电导率受无机基质中硼含量的影响。三氟甲磺酸根阴离子与硼的空p轨道之间的相互作用可以增强盐解离。这种相互作用似乎增加了锂离子迁移数。原位溶胶-凝胶加工是提供聚合离子液体的机械强度以及特定功能的一种有价值的方法。版权所有 (C) 2008 约翰·威利父子有限公司
Inorganic-organic composites that conduct lithium ions were prepared by in situ sol-gel processing, with polymerizable ionic liquids and functional silicate or borosilicate network. In the presence of lithium salts, radical polymerization of 1-ethyl-3-vinylimidazolium bis(trifluoromethane sulfonyl) imide ([evim][Tf2N]) was performed in parallel with the hydrolysis/polycondensation reaction of tetramethoxysilane (TMOS) with various trialkoxyboranes such as trimethoxyboran (TMOB), trii-sopropoxyborane (TiPOB) or mesityldimethoxyborane (Mes-DMOB). Many of the resulting composites were obtained as transparent or translucent glass-like solids. The composites had high decomposition temperatures above 300 degrees C, due to the high thermal stability of both the inorganic network and the polymerized ionic liquids. The ionic conductivity was increased by increasing the fraction of organic compounds. The ionic conductivity of the compound was also altered by the addition of LiTf2N, up to at least 10(-5); S cm(-1) at room temperature. The ionic conductivity of the LiSO3CF3 doped system was about one order of magnitude less than that. The ionic conductivity was found to be influenced by the boron content of the inorganic matrix. Interaction between the triflate anion and the empty p-orbital of boron may enhance the salt dissociation. This interaction appears to increase the lithium ion transference number. In situ sol-gel processing is a valuable way to provide mechanical strength, as well as specific functions, of polymerized ionic liquids. Copyright (C) 2008 John Wiley & Sons, Ltd.