Hongyi Zhang, Garrett L. Grocke, George Rose, Stuart J. Rowan, Shrayesh N. Patel
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引用次数: 0
Abstract
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-RAPGC 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-RAPGC yields the highest specific capacities, energy efficiency, and best kinetics at 0.1C. Conversely, C-rate dependence measurements show that DS-RAPEGA has higher specific capacities at faster C-rates and is more resilient to mass transport limitations compared to DS-RAPGC and DS-RAPMBA. This is attributed to greater electrolyte swelling in DS-RAPEGA 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.
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.