Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen

Kwak, Won‐Jin; Kim, Hun; Petit, Yann K.; Leypold, Christian; Nguyen, Trung Thien; Mahne, Nika; Redfern, Paul C.; Curtiss, Larry A.; Jung, Hun‐Gi; Borisov, Sergey M.; Freunberger, Stefan; Sun, Yang Kook

doi:10.1038/s41467-019-09399-0

Cited by 80 publications

(92 citation statements)

References 62 publications

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“…However, fluorescence quenching of DMA has not always been unambiguously observed during oxygen reduction in aprotic solvents containing lithium, although the detection of the endoperoxide at high DMA concentrations revealed the formation of 1 O 2 during Li‐O 2 cell discharge . Deactivation of redox mediators in lithium‐oxygen batteries by singlet oxygen has also been recently reported . Freiberg et al.…”

Section: Figurementioning

confidence: 99%

Singlet Oxygen Formation during the Oxygen Reduction Reaction in DMSO LiTFSI on Lithium Air Battery Carbon Electrodes

2019

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Formation of singlet oxygen,1O2, during the O2 electroreduction reaction (ORR) on carbon electrode in Lithium bis‐(tri‐fluoromethylsulfonyl)imide (LiTFSI) dimethyl sulfoxide (DMSO) electrolyte has been detected “in‐operando” by fluorescence quenching of 9,10‐dimethylanthracene, DMA. Furthermore, the formation of 1O2 during ORR requires Li+ ions, while in the presence of the efficient physical 1O2 quencher, sodium azide, DMA fluorescence quenching is negligible. Addition of Li+ ions to superoxide solution in DMSO formed by ORR enhances DMA quenching, which is a proof that 1O2 results from superoxide bimolecular disproportionation.

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Section: Figurementioning

confidence: 99%

Singlet Oxygen Formation during the Oxygen Reduction Reaction in DMSO LiTFSI on Lithium Air Battery Carbon Electrodes

2019

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“…[134,135] What's more, the majority of RMs suffers from severe decomposition toward singlet oxygen. [35,136] Therefore, to improve the efficiency of RM and battery stability, the exploration of RM immune from side reactions should be emphasized first. RM shuttling effect need to be avoided as well, using appropriate separation such as ceramic solid electrolyte, [135] metal-organic framework (MOF) separator, [137] and Al 2 O 3 /PVDF-HFP composite protective layer.…”

Section: Redox Mediatormentioning

confidence: 99%

Section: Singlet Oxygen: the Real Culprit For Parasitic Reactionsmentioning

confidence: 99%

“…However, some recent articles pointed that singlet oxygen instead of reactive oxygen species should be responsible for the degradation of carbon, electrolyte, and redox mediators (RMs). [34][35][36] Except for similar issues of Li dendrite and unstable solid-electrolyte interphase (SEI) layer in Li-metal batteries, Li metal suffers from serious corrosion in LOBs due to the active species diffusing from cathode. [37,38] These tricky problems urge researchers to pay more attention to understanding the parasitic reaction mechanism and exploring feasible strategies to suppress parasitic reaction.…”

Section: Introductionmentioning

confidence: 99%

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Challenges and Strategy on Parasitic Reaction for High‐Performance Nonaqueous Lithium–Oxygen Batteries

Zhang

Ding

et al. 2020

Advanced Energy Materials

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is restricted to their inferior energy densities (≈250 Wh kg −1) due to intercalation chemistry. Consequently, "beyond Li-ion batteries" such as lithium-sulfur batteries and metal-air batteries, which have fundamental discrepant energy storage mechanism, have been attracted worldwide attention recently. [4,5] Of all the candidates, rechargeable lithium-oxygen battery (LOB) is considered to be one of the most fascinating next-generation batteries with extremely high theoretical energy density (≈3500 Wh kg −1). [6,7] The low-cost and environmental positive active material oxygen originates from air, endowing LOBs more attractive to satisfy the soaring demand of large-scale energy storage system. Generally, there are four architecture systems of LOBs determined by different electrolyte: aqueous, nonaqueous, hybrid, and all-solid-state. [8-11] In 1996, Abraham and Jiang first reported the rechargeable lithium-oxygen battery consisted of Li metal anode, solid polymer electrolyte membrane, and composite carbon cathode. [12] After ten years, nonaqueous LOBs actually caught worldwide attention due to the outstanding capacity and reversibility. [6] A typical nonaqueous lithium-oxygen battery comprises a metallic Li anode, organic electrolyte containing Li salt, a separator, and a porous gas diffusion cathode loading with catalysts (Figure 1). [13] Generally, the electrochemical reactions of nonaqueous lithium-oxygen battery can be described as following equations [14-16] Overall reaction E 2Li O Li O 2.96 V vs Li/Li 2 2 2 () + ↔°= + (1) Cathodic process (oxygen reduction reaction (ORR))

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“…Although it has been recently demonstrated that the evolution of singlet oxygen during operation of Li-O 2 cell also leads to the degradations of cell components, reactive oxygen radical species remain one of the main causes of parasitic reactions, prohibiting the use of conventional electrolytes and air electrodes. [32][33][34][35][36] A breakthrough in the suppression of these side reactions is thus imperative to achieve stable operation of Li-O 2 batteries.…”

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confidence: 99%

Dual‐Functioning Molecular Carrier of Superoxide Radicals for Stable and Efficient Lithium–Oxygen Batteries

Bae

Song

Park

et al. 2020

Advanced Energy Materials

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Low round‐trip efficiency and poor cycle stability remain the major challenges associated with lithium–oxygen (Li–O2) batteries. These issues are primarily triggered by or correlated to the radical species produced during the operation of Li–O2 cells, which lead to significant deterioration of the electrolytes and air electrodes. Regulation of the reactivity of these radical species would thus open up opportunities to suppress such side reactions. Herein, a dual‐functioning molecule that is capable of mitigating the reactivity of radical species produced in a Li–O2 cell by reversibly forming stable intermediate complex during both the discharge and charge processes is introduced. Specifically, 5,5‐dimethyl‐1‐pyrroline N‐oxide (DMPO) is exploited, which has been widely used as a chemical agent to detect oxygen radicals, to induce the reversible formation of an intermediate complex, DMPO–O2−, in the presence of superoxide radicals. It is demonstrated that DMPO mediates the O2−‐involved electrochemical reaction, leading to significant suppression of side reactions and a remarkably improved oxygen efficiency. Unexpectedly, it is also observed that upon charging, DMPO actively scavenges the superoxides from the surface of discharge products, thus substantially lowering the charging overpotential. The combined radical mediation and scavenging of superoxides result in cycle stability of a practical Li–O2 cell over 200 cycles with a specific capacity of 1000 mAh g−1. The findings indicate the importance of controlling the reactivity of radical species and suggest a new pathway toward the realization of stable and efficient Li–O2 batteries.

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Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen

Cited by 80 publications

References 62 publications

Singlet Oxygen Formation during the Oxygen Reduction Reaction in DMSO LiTFSI on Lithium Air Battery Carbon Electrodes

Singlet Oxygen Formation during the Oxygen Reduction Reaction in DMSO LiTFSI on Lithium Air Battery Carbon Electrodes

Challenges and Strategy on Parasitic Reaction for High‐Performance Nonaqueous Lithium–Oxygen Batteries

Dual‐Functioning Molecular Carrier of Superoxide Radicals for Stable and Efficient Lithium–Oxygen Batteries

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