调整聚合物极性以调节有机电池氧化还原活性粒子中二硫化物的可及性

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-16 DOI:10.1021/acs.macromol.4c01894

Hongyi Zhang, Garrett L. Grocke, George Rose, Stuart J. Rowan, Shrayesh N. Patel

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引用次数: 0

摘要

本研究旨在探索颗粒极性与基于有机二硫化物的氧化还原活性颗粒的电化学可得性之间的关系。研究人员合成了微米大小的聚甲基丙烯酸缩水甘油酯（PMGA）颗粒，随后用二硫化硫噻二唑交联生成了氧化还原活性颗粒（DS-RAPs）。残留的缩水甘油单元与各种侧链发生反应，从而调节了 DS-RAPs 的极性。这些侧链从非极性的脂肪族 N-甲基丁胺（MBA）到极性更强的低聚乙二醇胺（EGA）和碳酸缩水甘油酯（GC）分子都有。循环伏安法显示，极性侧链的官能化提高了电化学亲和性，DS-RAPGC 在乙腈和四聚乙二醇基电解质中的亲和性最高。在使用 LiTFSI/四聚乙二醇电解质的锂电池中将 DS-RAP 衍生物作为阴极电极进行测试表明，DS-RAPGC 在 0.1C 时的比容量最高、能效最高、动力学性能最好。相反，与 C 速率相关的测量结果表明，与 DS-RAPGC 和 DS-RAPMBA 相比，DS-RAPEGA 在较快的 C 速率下具有更高的比容量，对质量传输限制的适应能力也更强。这是因为 DS-RAPEGA 的电解质溶胀性更强，离子扩散率更高，电静电间歇滴定技术 (GITT) 测量证明了这一点。最后，在 0.1C 下进行的长期循环测试表明，降解程度极小，由此导致的容量衰减归因于二硫化物在持续可逆氧化/还原过程中的电荷捕获。总之，这些研究结果极大地促进了用于储能应用的有效 RAPs 的开发，突出了通过侧链工程进行化学修饰在控制颗粒极性以增强电荷传输和整体电化学性能方面的关键作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Tailoring Polymer Polarity to Regulate Disulfide Accessibility in Redox-Active Particles for Organic Batteries

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Tailoring Polymer Polarity to Regulate Disulfide Accessibility in Redox-Active Particles for Organic Batteries

This study seeks to explore the relationship between particle polarity and the electrochemical accessibility of organo-disulfide-based redox-active particles. Micron-sized poly(glycidyl methacrylate) (PMGA) particles were synthesized and subsequently cross-linked with thiadiazole disulfide to produce redox-active particles (DS-RAPs). The residual glycidyl units underwent reactions with various side chains to modulate the polarity of the DS-RAPs. These side chains vary from nonpolar aliphatic N-methylbutylamine (MBA) to the more polar oligoethylene glycol amine (EGA) and glycidyl carbonate (GC) moieties. Cyclic voltammetry reveals that functionalization with polar side chains enhances electrochemical accessibility, with DS-RAP_GC demonstrating the highest accessibility in both acetonitrile and tetraglyme-based electrolytes. Testing the DS-RAP derivatives as cathode electrodes in a lithium cell with a LiTFSI/tetraglyme electrolyte indicates that DS-RAP_GC yields the highest specific capacities, energy efficiency, and best kinetics at 0.1C. Conversely, C-rate dependence measurements show that DS-RAP_EGA has higher specific capacities at faster C-rates and is more resilient to mass transport limitations compared to DS-RAP_GC and DS-RAP_MBA. This is attributed to greater electrolyte swelling in DS-RAP_EGA and higher ion diffusivity, as evidenced by galvanostatic intermittent titration technique (GITT) measurements. Lastly, long-term cycling tests at 0.1C indicate minimal degradation, with the resulting capacity fade attributed to charge trapping during the continuous reversible oxidation/reduction of disulfides. Overall, these findings contribute significantly to the development of effective RAPs for energy storage applications, highlighting the pivotal role of chemical modifications via side chain engineering in controlling particle polarity to enhance charge transport and overall electrochemical performance.

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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.