Solid polymer electrolytes based on polystyrene‐polyether block copolymers having branched ether structure
Solid polymer electrolytes based on polystyrene‐polyether block copolymers having branched ether structure
复制标题
DOI：
10.1002/pat.4511
复制
发表时间：
2018-12
影响因子：
3.4
通讯作者：
H. Kokubo;E. Nakazawa;M. Watanabe
中科院分区：
文献类型：
--
作者：
H. Kokubo;E. Nakazawa;M. Watanabe
为了获得具有高离子导电性和机械完整性的固体聚合物电解质(SPE)，我们采用一锅法阴离子聚合合成了聚苯乙烯(PST)-聚醚(PE)两嵌段共聚物。PST砌块有望在SPE中作为硬填料进行聚集，以提高力学性能。PE嵌段由不同摩尔比的环氧乙烷(EO)和2-(2-甲氧基乙氧基)乙基缩水甘油醚(MEEGE)的无规共聚物(P(EO-r-MEEGE))组成([EO]/[MEEGE]n=100/0、86/14、75/25、68/32和41/59)。PEO中MEEGE部分的引入降低了PEO的结晶度，MEEGE侧链的快速运动导致PE嵌段的塑化，从而促进了离子的快速传输。将得到的两嵌段共聚物(PSEx)与双(三氟甲磺酰基)胺锂(LiTFSA)按[Li]/[O]摩尔比混合，制得固相聚合物。所得SPE的离子电导率与PE嵌段中EO的摩尔比(X)和嵌段共聚物中PE嵌段的质量分数(FPE)有关。PSE0.86(FPE=0.65)具有与P(EO-r-MEEGE)(PE0.85；FPE=111.00)相当的高离子电导率(30°C时为3.3T×10−5S/cm−1；60°C时为1.1G×10−4S/cm−1)(30°C时为9.8×10−5S/cm−1；60°C时为4.0G×10−4S/cm−1)。
To obtain solid polymer electrolytes (SPEs) having high ionic conductivity together with mechanical integrity, we have synthesized polystyrene (PSt)‐polyether (PE) diblock copolymers via one‐pot anionic polymerization. The PSt block is expected to aggregate to act as hard fillers in the SPE to enhance the mechanical property. The PE block consists of random copolymer (P(EO‐r‐MEEGE)) of ethylene oxide (EO) and 2‐(2‐methoxyethoxy) ethyl glycidyl ether (MEEGE) in different molar ratios ([EO]/[MEEGE] = 100/0, 86/14, 75/25, 68/32, and 41/59). The introduction of the MEEGE moiety in PEO reduced the crystallinity of PEO, and the fast motion of the MEEGE side chain caused plasticization of the PE block, thereby contributing to the fast ion transport. SPEs were fabricated by mixing the obtained diblock copolymer (PSEx) and lithium bis(trifluoromethanesulfonyl) amide (LiTFSA) with [Li]/[O] = 0.05. Ionic conductivity of the obtained SPEs was dependent on the molar ratio of EO in the PE block (x) as well as the weight fraction of PE block (fPE) in the block copolymer. PSE0.86(fPE= 0.65) exhibited high ionic conductivity (3.3 × 10−5S cm−1at 30°C; 1.1 × 10−4S cm−1at 60°C) comparable with that of P(EO‐r‐MEEGE) (PE0.85;fPE= 1.00) (9.8 × 10−5S cm−1at 30°C; 4.0 × 10−4S cm−1at 60°C).