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磺酸基团在共价有机框架中的累积作为内在质子传导电解质。

Accumulation of Sulfonic Acid Groups Anchored in Covalent Organic Frameworks as an Intrinsic Proton-Conducting Electrolyte.

机构信息

Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou, 450007, P. R. China.

School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japan.

出版信息

Macromol Rapid Commun. 2022 Jan;43(1):e2100590. doi: 10.1002/marc.202100590. Epub 2021 Oct 18.

Abstract

Covalent organic frameworks (COFs) are a novel class of crystalline porous polymers, which possess high porosity, excellent stability, and regular nanochannels. 2D COFs provide a 1D nanochannel to form the proton transport channels. The abovementioned features afford a powerful potential platform for designing materials as proton transportation carriers. Herein, the authors incorporate sulfonic acid groups on the pore walls as proton sources for enhancing proton transport conductivity in the 1D channel. Interestingly, the sulfonic acid COFs (S-COFs) electrolytes being binder free exhibit excellent proton conductivity of ≈1.5 × 10 S cm at 25 ℃ and 95% relative humidity (RH), which rank the excellent performance in standard proton-conducting electrolytes. The S-COFs electrolytes keep the high proton conduction over the 24 h. The activation energy is estimated to be as low as 0.17 eV, which is much lower than most reported COFs. This research opens a new window to evolve great potential of structural design for COFs as the high proton-conducting electrolytes.

摘要

共价有机框架(COFs)是一类新型的结晶多孔聚合物,具有高孔隙率、优异的稳定性和规则的纳米通道。二维 COFs 提供了一维纳米通道,形成质子传输通道。上述特点为设计质子传输载体材料提供了强大的潜在平台。在此,作者将磺酸基团引入到孔壁中作为质子源,以增强一维通道中的质子传输电导率。有趣的是,无粘结剂的磺酸 COFs(S-COFs)电解质在 25℃和 95%相对湿度(RH)下表现出 ≈1.5×10-3 S cm 的优异质子电导率,在标准质子导电电解质中表现出优异的性能。S-COFs 电解质在 24 小时内保持高质子传导性。活化能估计低至 0.17 eV,远低于大多数报道的 COFs。这项研究为 COFs 作为高质子导电电解质的结构设计开辟了新的途径,展现出巨大的潜力。

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