Synthesis and Ring-Opening Polymerization of Functional Silacyclobutane Derivatives and Their Application to Lithium Ion Batteries
Synthesis and Ring-Opening Polymerization of Functional Silacyclobutane Derivatives and Their Application to Lithium Ion Batteries
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功能硅杂环丁烷衍生物的合成、开环聚合及其在锂离子电池中的应用
DOI：
10.1002/masy.201300234
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发表时间：
2015
影响因子：
--
通讯作者：
Takeshi Endo
中科院分区：
文献类型：
--
作者：
Kozo Matsumoto;Takeshi Endo
聚碳硅烷具有碳-硅骨架，是一种高度柔性的聚合物，具有优异的热稳定性、化学稳定性和电稳定性。它们可以通过硅杂环丁烷衍生物的开环聚合容易地制备。虽然聚硅杂环丁烷通常是非极性的，但通过引入5元环状碳酸酯结构作为侧基，它们可以与碳酸酯基电解质溶液相容，并且如果设计得当，它们可以作为制备凝胶聚合物电解质（GPE）的胶凝剂的有希望的候选物。我们设计了一种新的基于碳硅烷的GPE体系，其可以通过具有5元环状碳酸酯结构的硅环丁烷，4-{2-（1-甲基硅环丁基）}乙基-1，3-二氧戊环-2-酮（SBMC）的开环聚合来制备。GPE通过单体与交联剂1，6-双（1-甲基硅环丁基）己烷（HMBS）在由碳酸亚乙酯（EC）/碳酸二乙酯（DEC）混合溶剂中的1 M LiPF 6组成的电池电解质溶液中原位共聚而直接合成。所获得的GPE与通常的液体电解质相比显示出相对高的离子电导率，并且由该GPE构成的锂离子电池显示出与由通常的液体电解质构成的锂离子电池一样高的充/放电性能。
Polycarbosilanes, which have a carbon‐silicone backbone, are highly flexible polymers with excellent thermal, chemical, and electrical stability. They can be readily prepared by ring‐opening polymerization of silacyclobutane derivatives. Although polysilacycobutanes are non‐polar in general, they can be compatible to carbonate‐based electrolyte solutions by introducing a 5‐membered cyclic carbonate structure as a pendant group, and if properly designed they can be promising candidates as gelators to prepare gel polymer electrolytes (GPE). We designed a new carbosilane‐based GPE system, which could be prepared by ring‐opening polymerization of a silacyclobutane having a 5‐membered cyclic carbonate structure, 4‐{2‐(1‐methylsilacyclobutyl)}ethyl‐1,3‐dioxolane‐2‐one (SBMC). The GPEs were directly synthesized by copolymerization of the monomer with a crosslinker, 1,6‐bis(1‐methylsilacyclobutyl)hexane (HMBS), in situ of a battery electrolyte solution consisting of 1 M LiPF6in an ethylene carbonate (EC) / diethyl carbonate (DEC) mixed solvent. The obtained GPE showed relatively high ionic conductivity compared to usual liquid electrolytes, and the lithium ion batteries composed of this GPE showed charge/discharge performance as high as those composed of the usual liquid electrolyte.