结晶型PEO8∶NaPF6聚电解质中晶区链段的运动

doi:10.11938/cjmr20150102

波谱学杂志 ›› 2015, Vol. 32 ›› Issue (1): 12-22.doi: 10.11938/cjmr20150102

结晶型PEO8∶NaPF6聚电解质中晶区链段的运动

罗欢1,2，梁欣苗1,2，冯继文1，王立英1*

1. 波谱与原子分子物理国家重点实验室，武汉磁共振中心（中国科学院武汉物理与数学研究所），湖北武汉 430071；
2. 中国科学院大学，北京100049

收稿日期:2014-04-04 修回日期:2015-01-08 出版日期:2015-03-05 发布日期:2015-03-05
作者简介:罗欢(1984-)，男，湖北孝感人，博士研究生，分析化学专业. *通讯联系人：王立英，电话：027-87197794，E-mail：lywang@wipm.ac.cn.
基金资助:
国家自然科学基金资助项目(11004220，11274347).

Segmental Motion of PEO8∶NaPF6 Crystalline Polymer Electrolyte

LUO Huan1,2，LIANG Xin-miao1,2，FENG Ji-wen1，Wang Li-ying1*

1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Center for Magnetic Resonance (Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2014-04-04 Revised:2015-01-08 Online:2015-03-05 Published:2015-03-05
About author:*Corresponding author：WANG Li-ying, Tel: +86-27-87197794, E-mail: lywang@wipm.ac.cn.
Supported by:
国家自然科学基金资助项目(11004220，11274347).

摘要/Abstract

摘要：

利用固体NMR 研究了高度结晶的聚氧乙烯(PEO)/六氟磷酸钠(NaPF6)（按照氧钠摩尔比8∶1 描述为PEO8∶NaPF6，分子量Mw = 1 000 和6 000 g/mol）固体聚电解质晶区链段的结构和运动．对于纯PEO 来说，晶区链段的构象交换或大角度再取向促使其¹³C 粉末线形从低温的非轴对称(δ₃₃ < δ₂₂ < δ₁₁)变成高温的轴对称线形(δ₁₁ =δ₂₂ > δ₃₃)．通过变温的¹³C 粉末线形和243 K 下的二维交换谱，PEO8∶NaPF6 晶区链段同样存在大角度再取向，且开启温度也很低(~243 K)与PEO 接近．这种长程的运动使得PEO8∶NaPF6 从低温的类轴对称(δ₃₃ < δ₂₂ < δ₁₁)变成高温的轴对称线形(δ₃₃ > δ₂₂ = δ₁₁)，高温线形是PEO 高温线形的翻转．与其它PEO/Na(Li)固体聚电解质不同，PEO8∶NaPF6 中晶区链段与Na+络合后仍具有很高的运动性（与纯PEO 链段的运动性相当），这种高分子链段和Na+协同运动促使Na+沿PEO 分子链轴向迁移，提高电导率．

关键词: 固体核磁共振(solid-state NMR), 聚合物链段动力学, 电导率, 聚氧乙烯(PEO), PEO8∶NaPF6

Abstract:

Solid-state NMR spectroscopy was used to study the segmental motion of high-crystallinity PEO8∶NaPF6 electrolytes with different PEO molecular weights (Mw =1 000 and 6 000 g/mol, respectively). ¹³C-magic angle spinning (MAS) NMR spectra and static powder patterns, as well as static 2D exchange spectra, revealed that large-angle reorientation of the crystalline PEO segments in both PEO8∶NaPF6 complexes starts at a very low temperature (~243 K), similar to the case in pure crystalline PEO. At higher temperature, long-range reorientation gives rise to a well-defined high-temperature powder pattern of uniaxial chemical shift anisotropy (δ₃₃ > δ₂₂ = δ₁₁), perhaps as the result of flipping of PEO. In contrast to other PEO/Na (Li) solid electrolytes, the segments in crystalline PEO8∶NaPF6 are highly mobile even when coordinated with Na+, and this is comparable with PEO. It is suggested that the segmental motion in crystalline PEO8∶NaPF6 electrolyte can enhance ion transportation along the coil, improving ionic conductivity.

Key words: solid-state NMR, polymer dynamics, ionic conductivity, PEO, PEO8∶NaPF6

中图分类号:

O482.53

罗欢1,2，梁欣苗1,2，冯继文1，王立英1. 结晶型PEO8∶NaPF6聚电解质中晶区链段的运动[J]. 波谱学杂志, 2015, 32(1): 12-22.

LUO Huan1,2，LIANG Xin-miao1,2，FENG Ji-wen1，Wang Li-ying1. Segmental Motion of PEO8∶NaPF6 Crystalline Polymer Electrolyte[J]. Chinese Journal of Magnetic Resonance, 2015, 32(1): 12-22.

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结晶型PEO8∶NaPF6聚电解质中晶区链段的运动

Segmental Motion of PEO8∶NaPF6 Crystalline Polymer Electrolyte

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