How Does Nanoscale Crystalline Structure Affect Ion Transport in Solid Polymer Electrolytes?

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• 作者：Shan Cheng ; Derrick M. Smith ; Christopher Y. Li
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：June 24, 2014
• 年：2014
• 卷：47
• 期：12
• 页码：3978-3986
• 全文大小：491K
• ISSN：1520-5835

文摘

Polymer electrolytes have attracted intensive attention due to their potential applications in all-solid-state lithium batteries. Ion conduction in this system is generally considered to be confined in the amorphous polymer/ion phase, where segmental relaxation of the polymer above glass transition temperature facilitates ion transport. In this article, we show quantitatively that the effect of polymer crystallization on ion transport is twofold: structural (tortuosity) and dynamic (tethered chain confinement). We decouple these two effects by designing and fabricating a model polymer single crystal electrolyte system with controlled crystal structure, size, crystallinity, and orientation. Ion conduction is confined within the chain fold region and guided by the crystalline lamellae. We show that, at low content, due to the tortuosity effect, the in-plane conductivity is 2000 times greater than through-plane one. Contradictory to the general view, the dynamic effect is negligible at moderate ion contents. Our results suggest that semicrystalline polymer is a valid system for practical polymer electrolytes design.