电荷相关和离子溶剂化对SAXS/SANS单离子导电聚合物共混电解质相行为的影响

IF 5.2 1区 化学 Q1 POLYMER SCIENCE
Hsin-Ju Wu, Lilin He, William M. Breining, David M. Lynn and Whitney S. Loo*, 
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引用次数: 0

摘要

单离子导电聚合物共混物(SICPBs)作为固态电池电解质表现出优异的电化学性能;然而,它们的纳米尺度形态和热力学行为仍未被探索。在这项工作中,我们研究了由氘化聚(环氧乙烷)和聚[锂磺酰(三氟甲烷磺酰)亚胺甲基丙烯酸酯],dPEO/P(LiMTFSI)组成的共混物,并报道了首次使用小角中子散射(SANS)和小角x射线散射(SAXS)对电荷中性聚合物共混物纳米结构的实验研究。尽管单一的玻璃化转变温度表明了宏观上的混相,但SANS和SAXS的结果显示,共混物成分和温度强烈影响了无序的、电荷相关的纳米结构。在低浓度的电荷聚合物中,散射主要受浓度波动的影响,并采用随机相位近似提取Flory-Huggins相互作用参数χSC。在高电荷聚合物含量下,浓度波动被抑制,并使用相关模型来表征电荷相关的纳米结构。我们发现电荷相关的结构高度依赖于混合成分──与Sing的自一致场理论-液相模型的预测一致。了解这些特征对于揭示离子传输机制至关重要,离子传输机制可以改善SICPB系统的电化学性能。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

The Influence of Charge Correlation and Ion Solvation on the Phase Behavior of Single-Ion Conducting Polymer Blend Electrolytes Using SAXS/SANS

The Influence of Charge Correlation and Ion Solvation on the Phase Behavior of Single-Ion Conducting Polymer Blend Electrolytes Using SAXS/SANS

Single-ion conducting polymer blends (SICPBs) have demonstrated exceptional electrochemical performance as solid-state battery electrolytes; however, their nanoscale morphology and thermodynamic behavior remain unexplored. In this work, we investigate blends composed of deuterated poly(ethylene oxide) and poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate], dPEO/P(LiMTFSI), and report the first experimental study of the nanostructures of charge-neutral polymer blends using small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). Despite the macroscopic miscibility indicated by a single glass-transition temperature, SANS and SAXS results reveal disordered, charge-correlated nanostructures that are strongly influenced by blend composition and temperature. At low concentrations of charge polymer, the scattering is dominated by concentration fluctuations, and the random phase approximation is applied to extract values of the Flory–Huggins interaction parameter, χSC. At higher charged polymer content, concentration fluctuations are suppressed, and a correlation model is used to characterize the nanostructures of the charge correlations. We find that the structures of the charge correlations are highly dependent on blend composition─consistent with predictions from Sing’s self-consistent field theory-liquid state models. Understanding these features is essential for uncovering the ion transport mechanism that leads to improved electrochemical performance previously reported in SICPB systems.

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来源期刊
Macromolecules
Macromolecules 工程技术-高分子科学
CiteScore
9.30
自引率
16.40%
发文量
942
审稿时长
2 months
期刊介绍: Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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