Light-Switchable and Self-Healable Polymer Electrolytes Based on Dynamic Diarylethene and Metal-Ion Coordination
Light-Switchable and Self-Healable Polymer Electrolytes Based on Dynamic Diarylethene and Metal-Ion Coordination
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基于动态二芳基乙烯和金属离子配位的光开关和自修复聚合物电解质
DOI：
10.1021/jacs.0c11894
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发表时间：
2021
影响因子：
15
通讯作者：
Chabinyc, Michael L.
中科院分区：
文献类型：
--
作者：
Nie, Hui;Schauser, Nicole S.;Self, Jeffrey L.;Tabassum, Tarnuma;Oh, Saejin;Geng, Zhishuai;Jones, Seamus D.;Zayas, Manuel S.;Reynolds, Veronica G.;Chabinyc, Michael L.
据报道，基于动态 N 供体配体的二芳基乙烯 (DAE) 和多价 Ni2+ 金属离子配位，具有光可切换电导率的自修复聚合物电解质。具体来说，接枝有聚(乙二醇-r-DAE)丙烯酸酯共聚物侧链的聚苯乙烯聚合物与双(三氟甲磺酰亚胺)镍(II)(Ni(TFSI)2)盐有效交联，形成能够在温和条件下以快速交换动力学自修复的动态网络。此外，作为一种光开关化合物，DAE 会发生可逆的结构和电子重排，从而改变 DAE-Ni2+ 复合物在照射下的结合强度。这可以在含有 DAE 的聚合物电解质中观察到，其中紫外线照射会引发固体膜电阻的增加，而这种增加可以通过随后的可见光照射来恢复。紫外光照射下电阻的增加表明光开关后离子迁移率的降低，这与闭环DAE异构体与Ni2+更强的结合强度一致。1H–15N异核多重键相关核磁共振（HMBC NMR）光谱、连续波电子顺磁共振（cw EPR）光谱和密度泛函理论（DFT）计算证实了闭环DAE与金属之间的结合强度增加。流变学和原位离子电导率测量表明，这些聚合物电解质在损坏后可以有效修复以恢复其机械性能和离子电导率，这说明了其在智能电子产品中的潜在应用。
Self-healing polymer electrolytes are reported with light-switchable conductivity based on dynamicN-donor ligand-containing diarylethene (DAE) and multivalent Ni2+metal-ion coordination. Specifically, a polystyrene polymer grafted with poly(ethylene glycol-r-DAE)acrylate copolymer side chains was effectively cross-linked with nickel(II) bis(trifluoromethanesulfonimide) (Ni(TFSI)2) salts to form a dynamic network capable of self-healing with fast exchange kinetics under mild conditions. Furthermore, as a photoswitching compound, the DAE undergoes a reversible structural and electronic rearrangement that changes the binding strength of the DAE–Ni2+complex under irradiation. This can be observed in the DAE-containing polymer electrolyte where irradiation with UV light triggers an increase in the resistance of solid films, which can be recovered with subsequent visible light irradiation. The increase in resistance under UV light irradiation indicates a decrease in ion mobility after photoswitching, which is consistent with the stronger binding strength of ring-closed DAE isomers with Ni2+.1H–15N heteronuclear multiple-bond correlation nuclear magnetic resonance (HMBC NMR) spectroscopy, continuous wave electron paramagnetic resonance (cw EPR) spectroscopy, and density functional theory (DFT) calculations confirm the increase in binding strength between ring-closed DAE with metals. Rheological and in situ ion conductivity measurements show that these polymer electrolytes efficiently heal to recover their mechanical properties and ion conductivity after damage, illustrating potential applications in smart electronics.