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Efficient charge transport pathways in solutions of redox-active polymers are essential for advancing nextgeneration energy storage systems. Herein, we report the grafting of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate) (PTMA) polymer brushes onto silica particles with different molecular weights and grafting densities, and the impact of these composite particles in solutions of PTMA. The polymer-grafted particles are characterized using Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) techniques. The grafted polymers have molecular weights of 2.5 kDa and 5.0 kDa, with corresponding grafting densities of 0.688 and 0.378 chains nm−2 for SiO2-PTMA-2.5k and SiO2-PTMA-5k, respectively, with the grafting density decreasing with increasing graft length. To investigate the effect of these composite particles on charge transport in solutions of PTMA, different concentrations of the grafted particles were added to solutions of PTMA of different concentrations (near overlap concentration, C*) in 0.1 M LiTFSI in acetonitrile. Electrochemical analysis reveals that below C* the addition of SiO2-PTMA-5k increases the apparent diffusion coefficient (Dapp) 15.2% to 1.041 × 10−6 cm2 s−1 , the exchange rate constant (kex,app) by 9.5% to 1.546 × 1011 L mol−1 s−1, and the heterogeneous electron transfer rate constant (k0) by 24.6%, to 5.526 × 10−4 cm s−1. These results indicate that the synergistic interactions between unbound PTMA polymer chains in solution and PTMA-grafted particles facilitate interchain charge transfer kinetics. This highlights that grafted redoxactive particles can enhance charge transport without the limitations of polymer-only solutions (e.g., chain entanglement) and presents a promising design strategy for high-performance electrochemical applications, such as redox flow batteries (RFBs).
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Solvent mixtures for improved electron transfer kinetics of titanium-doped polyoxovanadate-alkoxide clusters
Emergent, flowable electrochemical energy storage technologies suitable for grid-scale applications are often limited by sluggish electron transfer kinetics that impede overall energy conversion efficiencies. To improve our understanding of these kinetic limitations in heterometallic charge carriers, we study the role of solvent in influencing the rates of heterogeneous electron transfer, demonstrating its impact on the kinetics of di-titanium substituted polyoxovanadate-alkoxide cluster, [Ti 2 V 4 O 5 (OMe) 14 ]. Our studies also illustrate that the one electron reduction and oxidation processes exhibit characteristically different rates, suggesting that different mechanisms of electron transfer are operative. We report that a 1 : 4 v/v mixture of propylene carbonate and acetonitrile can lead to a three-fold increase in the rate of electron transfer for one electron oxidation, and a two-fold increase in the one electron reduction process as compared to pure acetonitrile. We attribute this behavior to solvent–solvent interactions that lead to a deviation from ideal solution behavior. Coulombic efficiencies ≥90% are maintained in MeCN–PC mixtures over 20 charge/discharge cycles, greater than the efficiencies that are obtained for individual solvents. The results provide insight into the role of solvent in improving the rate of charge transfer and paves a way to systematically tune solvent composition to yield faster electron transfer kinetics.
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- PAR ID:
- 10436034
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 11
- Issue:
- 25
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 13729 to 13741
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3TA01179H
