Cordella Daniela, Ouhib Farid, Aqil Abdelhafid, Defize Thomas, Jérôme Christine, Serghei Anatoli, Drockenmuller Eric, Aissou Karim, Taton Daniel, Detrembleur Christophe
Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Department of Chemistry, University of Liege, Sart-Tilman B6A, 4000 Liege, Belgium.
Univ Lyon, Université Lyon 1, CNRS, Ingénierie des Matériaux Polymères, UMR 5223, F-69003 Lyon, France.
ACS Macro Lett. 2017 Feb 21;6(2):121-126. doi: 10.1021/acsmacrolett.6b00899. Epub 2017 Jan 20.
Poly(ionic liquid)s (PILs) have attracted considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Herein, we report the precise synthesis, characterization, and use as single-ion SPEs of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e., where all monomer units are of -vinyl-imidazolium type, with triethylene glycol pendant groups in the first block and a statistical distribution of -vinyl-3-ethyl- and -vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, by cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (TfN) for bromide (Br) counter-anions leads to PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σ = 1-3 × 10 S cm, as determined by broadband dielectric spectroscopy at 30 °C (under anhydrous conditions), and exhibit wide electrochemical stability (up to 4.8 V versus Li/Li) and form free-standing films with mechanical properties suited for SPE applications (Young's modulus = 3.8 MPa, elongation at break of 250%) as determined by stress/strain experiments.
聚离子液体（PILs）作为一种创新的单离子固体聚合物电解质（SPEs），已取代更为传统的电解质，在各种电化学装置中引起了广泛关注。在此，我们报道了一种新型的基于双PIL的两亲性二嵌段共聚物（BCP）的精确合成、表征及其作为单离子SPEs的应用，即所有单体单元均为乙烯基咪唑鎓型，第一嵌段带有三甘醇侧基，第二嵌段为乙烯基-3-乙基咪唑鎓溴化物和乙烯基-3-全氟辛基咪唑鎓溴化物的统计分布。通过钴介导的自由基聚合诱导自组装（CMR-PISA），在水中通过一锅法直接实现了BCP的合成。随后进行阴离子交换反应，用双（三氟甲基磺酰）亚胺（TfN）取代溴（Br）抗衡阴离子，得到了第一嵌段长度不同的PIL BCPs。通过30℃（无水条件下）的宽带介电谱测定，它们的离子电导率σ = 1 - 3×10 S cm，具有较宽的电化学稳定性（相对于Li/Li高达4.8 V），并且通过应力/应变实验测定，形成了具有适合SPE应用的机械性能的独立薄膜（杨氏模量 = 3.8 MPa，断裂伸长率为250%）。
