Proton trap effect on catechol–pyridine redox polymer nanoparticles as organic electrodes for lithium batteries

Gallastegui, Antonela; Minudri, Daniela; Casado, Nerea; Goujon, Nicolas; Ruipérez, Fernando; Patil, Nagaraj; Detrembleur, Christophe; Marcilla, Rebeca; Mecerreyes, David

doi:10.1039/d0se00531b

Cited by 19 publications

(24 citation statements)

References 38 publications

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“…The DFT calculation predicted a higher redox potential of P1 (3.5 V) than P2 (3.4 V) certainly because of the electron‐donating effects of methyl groups. The contradiction against the experimental results ( P1 : 3.3 and P2 : 3.5 V) may be explained by proton‐coupled redox reactions of P1 and other electrostatic interactions among the redox sites and electrolytes [6,33,39,40] …”

Section: Resultsmentioning

confidence: 69%

“…The contradiction against the experimental results (P1: 3.3 and P2: 3.5 V) may be explained by protoncoupled redox reactions of P1 and other electrostatic interactions among the redox sites and electrolytes. [6,33,39,40] Mulliken spin densities for the radical cations of 2, 4, and 5 were visualized to rationalize the electrochemical stability of the molecules (Figures 4 and S12). In dimethylfluoflavin 2, the most robust compound in this study, radical spins were located mainly on nitrogen atoms connected to methyl groups.…”

Section: Resultsmentioning

confidence: 99%

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Quadruply Fused Aromatic Heterocycles toward 4 V‐Class Robust Organic Cathode‐Active Materials

Hatakeyama‐Sato

Akahane

et al. 2022

Batteries & Supercaps

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Quadruply fused aromatic heterocycles are examined as 4 V‐class organic cathode‐active materials. A newly synthesized dimethylfluoflavin‐substituted polymer displays reversible charge/discharge at high potentials of 3.5 and 4.1 V (vs. Li/Li+) as a cathode‐active material for organic secondary batteries. The robust redox‐active heterocycles enable the long cycle‐life (>1000) while maintaining the high potential over 4 V. The linear polymer backbone and radical spin configuration in the heterocycles are the keys to enhancing the voltages and the cycle life.

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Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Quadruply Fused Aromatic Heterocycles toward 4 V‐Class Robust Organic Cathode‐Active Materials

Hatakeyama‐Sato

Akahane

et al. 2022

Batteries & Supercaps

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“…Thus, four different sizes of poly(dopamine methacrylamide) homopolymer particles were synthesized: cRPN-30, cRPN-60, cRPN-100 and cRPN-165, of which three of them were synthesized with surfactant and cRPN-165 without. [23] The hydrodynamic diameter of the cRPNs within the aqueous latex was determined by DLS and their dried size by Transmission Electron Microscopy (TEM). As observed in Table S1, the cRPNs showed a particle size from 165 nm to a very small ones of 30 nm.…”

Section: Synthesis and Characterization Of Catechol Redox-active Poly...mentioning

confidence: 99%

“…[20,21] Another interesting possibility to avoid further dissolution of the organic material is the use of cross-linked redox polymer nanoparticles (RPNs). [22,23] Due to the versatility of polymer chemistry, RPNs can be designed with different different redox active groups (e. g., quinones, nitroxides) [24,25] and sizes from nanometer to micrometer. This versatility makes RPNs excellent candidates for different electrochemical applications.…”

Section: Introductionmentioning

confidence: 99%

Aging Effect of Catechol Redox Polymer Nanoparticles for Hybrid Supercapacitors

Gallastegui

Camara

Minudri

et al. 2022

Batteries & Supercaps

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Redox-polymer nanoparticles are a promising solution to avoid the detrimental dissolution of organic electrode materials while showing discrete redox processes. In this work, catechol-based redox-active polymer nanoparticles (cRPNs) were synthesized through one-step emulsion polymerization with a tunable size from 25 to 150 nm. The fresh cRPNs were characterized and showed a reversible redox process centered at 0.50 V (vs. Ag/ AgCl) in 1 M H 2 SO 4 . Unexpectedly, the cRPN latex aged after days passing from white to pink. This aging resulted in a shift of its redox potential toward higher values, which could be associated to autoxidation of the catechol groups and subsequent crosslinking of NPs due to catechol dimer formation. Finally, we compared the performance of fresh and aged cRPNs in a hybrid supercapacitor device, proving how the aging effect had some benefits such as an increase in the voltage output, specific capacitance, cyclability and Coulombic efficiencies of the device.

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“…Finally, redox polymers can be designed using a wide range of polymerization methods such as free-radical polymerization, controlled radical polymerization or emulsion polymerization, allowing high tuneability of their macromolecular architecture to suit application requirements. Interestingly, the use of redox polymer nanoparticles has been recently shown to have a beneficial impact on the rate capability of redox polymer electrodes, where higher capacity retention was observed at fast (dis-) charge rate with smaller nanoparticles (i.e., <200 nm) [15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Chemical Upcycling of PET Waste towards Terephthalate Redox Nanoparticles for Energy Storage

Goujon

Demarteau

Pariza

et al. 2021

Sustainable Chemistry

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Over 30 million ton of poly(ethylene terephthalate) (PET) is produced each year and no more than 60% of all PET bottles are reclaimed for recycling due to material property deteriorations during the mechanical recycling process. Herein, a sustainable approach is proposed to produce redox-active nanoparticles via the chemical upcycling of poly(ethylene terephthalate) (PET) waste for application in energy storage. Redox-active nanoparticles of sizes lower than 100 nm were prepared by emulsion polymerization of a methacrylic-terephthalate monomer obtained by a simple methacrylate functionalization of the depolymerization product of PET (i.e., bis-hydroxy(2-ethyl) terephthalate, BHET). The initial cyclic voltammetry results of the depolymerization product of PET used as a model compound show a reversible redox process, when using a 0.1 M tetrabutylammonium hexafluorophosphate/dimethyl sulfoxide electrolyte system, with a standard redox potential of −2.12 V vs. Fc/Fc+. Finally, the cycling performance of terephthalate nanoparticles was investigated using a 0.1 M TBAPF6 solution in acetonitrile as electrolyte in a three-electrode cell. The terephthalate anode electrode displays good cycling stability and performance at high C-rate (i.e., ≥5C), delivering a stable specific discharge capacity of 32.8 mAh.g−1 at a C-rate of 30 C, with a capacity retention of 94% after 100 cycles. However, a large hysteresis between the specific discharge and charge capacities and capacity fading are observed at lower C-rate (i.e., ≤2C), suggesting some irreversibility of redox reactions associated with the terephthalate moiety, in particular related to the oxidation process.

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Proton trap effect on catechol–pyridine redox polymer nanoparticles as organic electrodes for lithium batteries

Abstract: New redox-active polymer nanoparticles present that the redox potential of the catechol group is affected by the presence of the pyridine. This positive potential gain is associated to the proton trap effect, which benefits the performance of lithium-ion–polymer batteries.

Cited by 19 publications

References 38 publications

Quadruply Fused Aromatic Heterocycles toward 4 V‐Class Robust Organic Cathode‐Active Materials

Quadruply Fused Aromatic Heterocycles toward 4 V‐Class Robust Organic Cathode‐Active Materials

Aging Effect of Catechol Redox Polymer Nanoparticles for Hybrid Supercapacitors

Chemical Upcycling of PET Waste towards Terephthalate Redox Nanoparticles for Energy Storage

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