A dismutase-biomimetic bifunctional mobile catalyst for anti-aging lithium–oxygen batteries

Kim, Jonghak; Jung, Gwan Yeong; Hwang, Chihyun; Jeong, Jinhyeon; Baek, Kyungeun; Lee, Jeongin; Kang, Seok Ju; Kwak, Sang Kyu; Song, Hyun‐Kon

doi:10.1016/j.jpowsour.2021.229633

Cited by 10 publications

(13 citation statements)

References 42 publications

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“…The retention time of superoxide in electrolyte was reduced in the presence of AAT so that the chances of superoxide challenging solvent molecules and/or AAT were limited. The superoxide-solvating AAT could be considered to be a superoxide dismutase mimics (SODm) we have reported in terms of boosting the kinetics of superoxide disproportionation reaction. ,, …”

Section: Resultsmentioning

confidence: 99%

Amphi-Active Superoxide-Solvating Charge Redox Mediator for Highly Stable Lithium–Oxygen Batteries

Kim

Jeong

Jung

et al. 2022

ACS Appl. Mater. Interfaces

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A multifunctional electrolyte additive for lithium oxygen batteries (LOBs) was designed to have (1) a redox-active moiety to mediate decomposition of lithium peroxide (Li2O2 as the final discharge product) during charging and (2) a solvent moiety to solvate and stabilize lithium superoxide (LiO2 as the intermediate discharge product) in electrolyte during discharging. 4-Acetamido-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-yl)oxyl) or AAT was employed as the additive working for both charge and discharge processes (amphi-active). The redox-active moiety was rooted in TEMPO, while the acetamido (AA) functional group inherited the high donor number (DN) of N,N-dimethylacetamide (DMAc). Integrating two functional moieties (TEMPO and AA) into a single molecule resulted in the bifunctionality of AAT (1) facilitating Li2O2 decomposition by the TEMPO moiety and (2) encouraging the solvent mechanism of Li2O2 formation by the high-DN AA moiety. Significantly improved LOB performances were achieved by the superoxide-solvating charge redox mediator, which were not obtained by a simple cocktail of TEMPO and DMAc.

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Section: Resultsmentioning

confidence: 99%

Amphi-Active Superoxide-Solvating Charge Redox Mediator for Highly Stable Lithium–Oxygen Batteries

Kim

Jeong

Jung

et al. 2022

ACS Appl. Mater. Interfaces

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“…This SODR is responsible for the latter part of oxygen reduction reaction (ORR) especially in solution mechanism during LOB discharge. 20,21 The SODR (eq 4) following the superoxide formation reaction (eq 1) completes lithium peroxide formation reaction from oxygen during discharge.…”

Section: Introductionmentioning

confidence: 99%

Shifting Target Reaction from Oxygen Reduction to Superoxide Disproportionation by Tuning Isomeric Configuration of Quinone Derivative as Redox Mediator for Lithium–Oxygen Batteries

Kim

Lee

Jeong

et al. 2022

ACS Appl. Mater. Interfaces

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Quinones having a fully conjugated cyclic dione structure have been used as redox mediators in electrochemistry. 2,5-Ditert-butyl-1,4-benzoquinone (DBBQ or DB-p-BQ) as a para-quinone derivative is one of the representative discharge redox mediators for facilitating the oxygen reduction reaction (ORR) kinetics in lithium−oxygen batteries (LOBs). Herein, we presented that the redox activity of DB-p-BQ for electron mediation was possibly used for facilitating superoxide disproportionation reaction (SODR) by tuning the isomeric configuration of the carbonyl groups of the substituted quinone to change its reduction potentials. First, we expected a molecule having its reduction potential between oxygen/superoxide at 2.75 V versus Li/Li + and superoxide/peroxide at 3.17 V to play a role of the SODR catalyst by transferring an electron from one superoxide (O 2 − ) to another superoxide to generate dioxygen (O 2 ) and peroxide (O 2 2− ). By changing the isomeric configuration from para (DB-p-BQ) to ortho (DB-o-BQ), the reduction potential of the first electron transfer (Q/Q − ) of the ditert-butyl benzoquinone shifted positively to the potential range of the SODR catalyst. The electrocatalytic SODRpromoting functionality of DB-o-BQ kept the reactive superoxide concentration below a harmful level to suppress superoxidetriggered side reaction, improving the cycling durability of LOBs, which was not achieved by the para form. The second electron transfer process (Q − / Q 2− ) of the DB-o-BQ, even if the same process of the para form was not used for facilitating ORR, played a role of mediating electrons between electrode and oxygen like the Q/Q − process of the para form. The ORR-promoting functionality of the ortho form increased the LOB discharge capacity and reduced the ORR overpotential.

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“…Generally, the produced lithium oxides will be deposited on the cathode surface during the discharge process and decompose and Li + ions return to the lithium anode during the charge process. 11,12 However, the product cannot decompose completely and will always remain on the surface of the cathodes even if being overcharged. 13,14 During cycles, the formed lithium oxides will accumulate on the surface of cathodes, decreasing the conductivity of the electrode and blocking the transport of oxygen, which reduces the reactive sites and even stops the electrode reaction as oxygen cannot be accessible.…”

Section: Introductionmentioning

confidence: 99%

“…The oxygen electrode, also called the air electrode, acts as a cathode in a lithium-oxygen battery to focus on the transport of oxygen and the reaction between oxygen and lithium ions. Generally, the produced lithium oxides will be deposited on the cathode surface during the discharge process and decompose and Li + ions return to the lithium anode during the charge process. , However, the product cannot decompose completely and will always remain on the surface of the cathodes even if being overcharged. , During cycles, the formed lithium oxides will accumulate on the surface of cathodes, decreasing the conductivity of the electrode and blocking the transport of oxygen, which reduces the reactive sites and even stops the electrode reaction as oxygen cannot be accessible. , Thus, it is critical to increase the specific surface area and reactive sites of the cathode, and various porous materials have been investigated as oxygen electrodes. Among various porous materials, metal organic framework (MOF) materials have received extensive attention because of their many advantages, such as a high specific surface area, high porosity, and unique microstructure. , As a typical zeolite imidazole ester framework material, ZIF-67 is usually formed from the self-assembly of Co 2+ and 2-methylimidazole through coordination , and can be further converted into porous carbon doped with nitrogen while being calcined in an inert atmosphere .…”

Section: Introductionmentioning

confidence: 99%

Binder-Free Flexible Three-Dimensional Porous Electrodes by Combining Microstructures and Catalysis to Enhance the Performance of Lithium-Oxygen Batteries

Yang

Chen

et al. 2021

Ind. Eng. Chem. Res.

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Metal-air batteries are promising for the next-generation energy storage because of attractive energy density, but they also face great challenges for applications. To intensify transfer and increase reaction active sites as well as decrease polarization, binder-free flexible three-dimensional porous oxygen electrodes were prepared by in situ deposition and decomposition of ZIF-67 on graphite foam (GF). Compared with GF, the modified sample has a much more stable discharge platform, lower charge/discharge polarization, higher reversibility, and higher reaction activity during oxygen reduction reaction and oxygen evolution reaction processes. The current densities of the reduction peak and oxidation peak of the pristine GF can be improved by a ZIF-67 derivative about 794 and 1367%, respectively. After 100 cycles at 0.1 mA·cm–2, the R ct of GF is decreased about 52% by the ZIF-67 derivative. The work paves a promising strategy for oxygen electrodes by combining absorption and electrocatalysis.

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A dismutase-biomimetic bifunctional mobile catalyst for anti-aging lithium–oxygen batteries

Cited by 10 publications

References 42 publications

Amphi-Active Superoxide-Solvating Charge Redox Mediator for Highly Stable Lithium–Oxygen Batteries

Amphi-Active Superoxide-Solvating Charge Redox Mediator for Highly Stable Lithium–Oxygen Batteries

Shifting Target Reaction from Oxygen Reduction to Superoxide Disproportionation by Tuning Isomeric Configuration of Quinone Derivative as Redox Mediator for Lithium–Oxygen Batteries

Binder-Free Flexible Three-Dimensional Porous Electrodes by Combining Microstructures and Catalysis to Enhance the Performance of Lithium-Oxygen Batteries

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