全两性离子聚合物支持的离子凝胶电解质，具有疏水性离子液体,The Journal of Physical Chemistry B

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全两性离子聚合物支持的离子凝胶电解质，具有疏水性离子液体
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2018-08-24 , DOI: 10.1021/acs.jpcb.8b05985
Morgan E. Taylor ₁ , Matthew J. Panzer ₁

Affiliation

在此报告中，已通过在疏水离子液体1-乙基-3中使用2-甲基丙烯酰氧基乙基磷酰胆碱（MPC）和磺基甜菜碱乙烯基咪唑（SBVI）的各种摩尔比，通过原位光聚合合成了用于离子凝胶电解质的全两性离子（ZI）共聚物支架。 -甲基咪唑双（三氟甲基磺酰基）酰亚胺（EMI TFSI）。根据ZI支架的化学成分，发现离子凝胶室温离子电导率在2.5至6.7 mS cm ^–1之间变化在固定的总聚合物含量为20 mol％的情况下。压缩弹性模量也表现出对共聚单体比率的强烈依赖性，由于ZI物理交联度的不同，观察到的值在23 kPa和11 MPa之间。这些结果以及NMR化学位移分析表明，MPC的磷酸胆碱ZI基团与EMI TFSI相互作用更强，而SBVI倾向于自聚集并在离子液体（IL）中形成偶极-偶极交联。EMI ⁺阳离子和TFSI的自扩散测量^–离子凝胶和ZI溶液样品中的阴离子证实，在包含MPC的系统中较慢的离子扩散是由于两性离子/ IL相互作用引起的，而不仅仅是在聚合物支架存在下迁移率降低。这项工作突出了相对两性离子/ IL和ZI偶极-偶极相互作用对新型新型完全由ZI聚合物支撑的含疏水IL的离子支撑电解质的性能的重要性，该电解质适用于未来的电能存储应用。

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Fully-Zwitterionic Polymer-Supported Ionogel Electrolytes Featuring a Hydrophobic Ionic Liquid

In this report, fully-zwitterionic (ZI) copolymer scaffolds for ionogel electrolytes have been synthesized via in situ photopolymerization using various molar ratios of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine vinylimidazole (SBVI) within the hydrophobic ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI). Depending on the chemical composition of the ZI scaffold, ionogel room temperature ionic conductivities are found to vary between 2.5 and 6.7 mS cm^–1 at a fixed 20 mol % total polymer content. Compressive elastic moduli also exhibit a strong dependence on the co-monomer ratio, with values between 23 kPa and 11 MPa observed because of different degrees of ZI physical cross-linking. These results, together with NMR chemical shift analysis, suggest that the phosphorylcholine ZI group of MPC interacts more strongly with EMI TFSI, while SBVI prefers to self-aggregate and form dipole–dipole cross-links in the ionic liquid (IL). Self-diffusivity measurements of the EMI⁺ cations and TFSI^– anions in both ionogel and ZI solution samples confirm that slower ion diffusion in MPC-containing systems is due to attractive zwitterion/IL interactions, and not merely reduced mobility in the presence of a polymeric scaffold. This work highlights the importance of relative zwitterion/IL and ZI dipole–dipole interactions on the properties of a novel class of fully-ZI polymer-supported ionogel electrolytes containing a hydrophobic IL suitable for future electrical energy storage applications.

更新日期：2018-08-24

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