Solid Polymer Electrolytes with Excellent High-Temperature Properties Based on Brush Block Copolymers Having Rigid Side Chains
Solid Polymer Electrolytes with Excellent High-Temperature Properties Based on Brush Block Copolymers Having Rigid Side Chains
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基于具有刚性侧链的刷状嵌段共聚物的具有优异高温性能的固体聚合物电解质
DOI：
10.1021/acsami.6b15893
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发表时间：
2017
影响因子：
9.5
通讯作者：
Fan Xing-He
中科院分区：
文献类型：
--
作者：
Ping Jing;Pan Hongbing;Hou Ping-Ping;Zhang Meng-Yao;Wang Xing;Wang Chao;Chen Jitao;Wu Decheng;Shen Zhihao;Fan Xing-He
通过串联开环易位聚合合成了一系列具有聚降冰片烯主链、聚{2,5-双[(4-甲氧基苯基)氧羰基]苯乙烯}（PMPCS，刚性链）和聚环氧乙烷（PEO）侧链的刷状嵌段共聚物（BBCP）。 BBCP 中 PEO 的重量分数相似，PEO 侧链的聚合度 (DP) 相同，而 PMPCS 的 DP 不同。通过小角 X 射线散射 (SAXS) 研究了块体自组装行为。整齐的 BBCP 不能形成有序的纳米结构。然而，掺杂锂盐后，BBCP 自组装成层状（LAM）结构。当PEO和PMPCS侧链的DP相似时，LAM结构更加有序，这归因于PMPCS和PEO相之间的界面更加平坦。测量了具有最有序LAM结构的BBCP/锂盐络合物在不同温度下的离子电导率（σ）值。在 40-200 °C 范围内，σ 值随着温度的升高而增大，并且 σ 和 T 之间的关系符合 Vogel-Tamman-Fulcher (VTF) 方程。 200℃时的σ值为1.58×10-3S/cm，这是PEO基聚合物电解质的最高值之一。这些在高温下具有高σ值的材料可用于高温锂离子电池。
A series of brush block copolymers (BBCPs) with polynorbornene backbones containing poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS, which is a rigid chain) and poly(ethylene oxide) (PEO) side chains were synthesized by tandem ring-opening metathesis polymerizations. The weight fractions of PEO in BBCPs are similar, and the degrees of polymerization (DPs) of PEO side chains are the same while the DPs of PMPCS are different. The bulk self-assembling behaviors were studied by small-angle X-ray scattering (SAXS). The neat BBCPs cannot form ordered nanostructures. However, after the doping of lithium salt, the BBCPs self-assemble into lamellar (LAM) structures. When the DPs of the PEO and PMPCS side chains are similar, the LAM structure is more ordered, which is attributed to the more flat interface between PMPCS and PEO phases. The ionic conductivity (σ) values of the BBCP/lithium salt complex with the most ordered LAM structure at different temperatures were measured. The σ value increases with increasing temperature in the range of 40–200 °C, and the relationship between σ andTfits the Vogel–Tamman–Fulcher (VTF) equation. The σ value at 200 °C is 1.58 × 10–3S/cm, which is one of the highest values for PEO-based polymer electrolytes. These materials with high σ values at high temperatures may be used in high-temperature lithium ion batteries.