Tuning phase transition and ferroelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) via grafting with desired poly(methacrylic ester)s as side chains
Tuning phase transition and ferroelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) via grafting with desired poly(methacrylic ester)s as side chains
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通过接枝所需的聚（甲基丙烯酸酯）作为侧链来调节聚（偏二氟乙烯-三氟乙烯）的相变和铁电性能
DOI：
10.1039/c2tc00431c
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发表时间：
2013-01-01
影响因子：
6.4
通讯作者：
Zhang, Zhicheng
中科院分区：
文献类型：
--
作者：
Li, Junjie;Hu, Xin;Zhang, Zhicheng
为了在高能量密度和低能量损耗的高储能电容器中具有潜在的应用前景，设计并研究了三组聚偏氟乙烯-三氟乙烯-三氟氯乙烯共聚物[P（VDF-TrFE-CTFE）]接枝聚甲基丙烯酸酯共聚物，包括聚甲基丙烯酸甲酯（PMMA）、聚甲基丙烯酸乙酯（PEMA）和聚甲基丙烯酸丁酯（PBMA）。由于聚甲基丙烯酸酯链段具有中等极性、较高的玻璃化转变温度以及与PVDF链段的良好相容性，其引入不仅可以显著削弱取向极性晶体间的耦合作用，而且可以加速极性晶畴沿着电场方向的反转，从而产生良好的剩余极化。结果表明，在高电场作用下，接枝共聚物的位移-电场（D-E）滞回行为可以从典型的铁电性转变为反铁电性或线性。同时，显著降低了能量损失，有效提高了能量释放效率。与PMMA和PBMA相比，具有中等极性和中等接枝长度的PEMA对P（VDF-TrFE-CTFE）的F-P跃迁具有更好的限制作用，从而使共聚物具有更好的储能性能。这些发现有助于深入理解PVDF基氟聚合物的铁电性质，并设计具有高放电能量密度和低能量损耗的新型储能电容器材料。
For potential application in high energy storage capacitors with high energy density and low energy loss, three sets of poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] grafted with poly(methacrylic ester)s, including poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(butyl methacrylate) (PBMA) copolymers, are designed and investigated carefully. Due to their intermediate polarity, relatively high glass transition temperature, and excellent compatibility with PVDF chains, the poly(methacrylic ester) segments introduced could not only dramatically weaken the coupling interactions of oriented polar crystals, but could also accelerate the reversal switching of polar crystal domains along the applied electric field, which leads to well hindered remnant polarization. As a result, the displacement–electric field (D–E) hysteresis behaviors of the graft copolymers could be tuned from typical ferroelectric to either antiferroelectric or linear shape under high electric field. Meanwhile, significantly reduced energy loss and effectively improved energy discharging efficiency were obtained. Compared with PMMA and PBMA, PEMA with intermediate polarity and grafting length exhibits more suitable confinement of the F–P transition of P(VDF-TrFE-CTFE), and thus more desirable energy storage properties are observed in the resultant copolymers. These findings may help to deeply understand the ferroelectric nature of PVDF based fluoropolymers and design new energy storage capacitor materials with high discharged energy density and low energy loss.