Hierarchical Ion-Conducting Materials Based on Polymer-Aligned Nanoparticles within Poly(vinyl benzyl methoxy poly(ethylene oxide) ether)- block -polystyrene Diblock Copolymer

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-16 DOI:10.1021/acs.macromol.6c01855

Leire Unanue,Monika Król,Gabriele Lingua,Jorge L. Olmedo-Martínez,Alejandro Herranz Berzosa,Sven Schneider,Agnieszka Tercjak,Janne Ruokolainen,Patrick Théato,Alejandro J. Müller,David Mecerreyes

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Abstract

Abstract Solid polymer electrolytes based on poly(ethylene oxide) (PEO) are promising alternatives to liquid electrolytes for safer lithium-ion batteries. Here, we report hierarchical solid polymer electrolytes obtained by selectively incorporating lithium sulfonamide-functionalized polymer nanoparticles (LiNPs) into a microphase-separated poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-block-polystyrene block copolymer. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) demonstrate that the phase-segregated lamellar morphology of the block copolymer is preserved upon nanoparticle incorporation. Notably, the LiNPs preferentially localize within the poly(ethylene glycol)-rich lamellae, generating hierarchical structures with ordering across multiple length scales arising from block copolymer self-assembly, selective nanoparticle organization, and poly(ethylene glycol) crystallization. Differential scanning calorimetry (DSC) reveals that the crystallinity of the poly(ethylene glycol) phase depends strongly on nanoparticle loading and plasticizer content. These hierarchical electrolytes exhibit high ionic conductivity, which is further enhanced by the addition of sulfolane as a plasticizer. These results elucidate the interplay between hierarchical morphology, phase crystallinity, and ion transport in block copolymer-based solid electrolytes, providing design guidelines for mechanically robust solid electrolytes with enhanced transport performance.

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基于聚（乙烯基苄基甲氧基聚（环氧乙烷）醚）-嵌段-聚苯乙烯二嵌段共聚物内聚合物取向纳米颗粒的分级离子导电材料

基于聚环氧乙烷（PEO）的固体聚合物电解质是一种有前途的液体电解质替代品，可用于更安全的锂离子电池。在这里，我们报告了通过选择性地将磺胺锂功能化聚合物纳米颗粒（LiNPs）加入微相分离的聚（乙烯苄基甲氧基聚（环氧乙烷）醚）-嵌段-聚苯乙烯嵌段共聚物中获得的分层固体聚合物电解质。透射电子显微镜（TEM）、原子力显微镜（AFM）和小角度x射线散射（SAXS）表明，纳米颗粒掺入后，嵌段共聚物的相分离层状形貌得以保留。值得注意的是，LiNPs优先定位于富含聚乙二醇的片层内，通过嵌段共聚物自组装、选择性纳米颗粒组织和聚乙二醇结晶，在多个长度尺度上产生有序的层次结构。差示扫描量热法（DSC）表明，聚乙二醇相的结晶度很大程度上取决于纳米颗粒的负载和增塑剂的含量。这些分层电解质表现出高离子电导率，这是进一步加强了添加磺烷作为增塑剂。这些结果阐明了嵌段共聚物固体电解质中层次形态、相结晶度和离子传输之间的相互作用，为具有增强传输性能的机械坚固固体电解质的设计提供了指导。

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来源期刊

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.