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

Córdoba, Daniel; Rodríguez, Hernán B.; Calvo, Ernesto J.

doi:10.1002/slct.201904112

Cited by 26 publications

(50 citation statements)

References 29 publications

(31 reference statements)

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“…For example, the absorption/emission spectra of DMA appear 300–700 nm region, and their signals are reduced after capturing 1 O 2 via [4+2] cycloaddition (Figure 4c) [5b] . Various examples of adapting trapping agents to Li−O 2 and Na–O 2 cells are summarized in Table S1 [5,13a,14,21,22,24,26,31] in the Supporting Information. Delithiated lithium iron phosphate (Li 1− x FePO 4 ) was used as the anode to avoid unintended decomposition of the trapping agents.…”

Section: Detection Of 1o2 In Li−o2 Cellsmentioning

confidence: 99%

Singlet Oxygen in Lithium−Oxygen Batteries

Hong

Byon

2020

Batteries & Supercaps

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Singlet oxygen (1O2) is one of the most critical species leading to parasitic side reactions and poor reversibility in non‐aqueous Li−O2 batteries. 1O2 is generated via the disproportionation of the superoxide radical (O2.−) in O2/Li2O2 electrochemistry. The mechanistic and computational studies on 1O2 formation revealed the significant roles of the associated cations, solvation ability of aprotic solvents, H+ source, and catalyst/electrode materials. Along with efforts to alleviate 1O2 production, trapping and eliminating 1O2 have been attempted using molecular agents. Anthracene derivatives trap 1O2 and form endoperoxides, which can be quantitatively detected using in situ fluorescence analysis. Physical quenchers that convert 1O2 to 3O2 are desirable for cycling of Li−O2 cells because quencher molecules are reusable. We highlight the recent reports on the formation and elimination of 1O2, and challenges and perspectives of suppressing the 1O2 effect on the performance of Li−O2 cells.

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Section: Detection Of 1o2 In Li−o2 Cellsmentioning

confidence: 99%

Singlet Oxygen in Lithium−Oxygen Batteries

Hong

Byon

2020

Batteries & Supercaps

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“…S3) [27]. The method is now the widely adopted standard method to detect 1 O2 in nonaqueous electrochemical environments [17,27,28,34,[36][37][38].…”

Section: Resultsmentioning

confidence: 99%

Surface and Catalyst Driven Singlet Oxygen Formation in Li-O2 Cells

Samojlov¹,

Schuster²,

Kahr³

et al. 2020

Preprint

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Large overpotentials upon discharge and charge of Li-O2 cells have motivated extensive research into heterogeneous solid electrocatalysts or non-carbon electrodes with the aim to improve rate capability, round-trip efficiency and cycle life. These features are equally governed by parasitic reactions, which are now recognized to be caused by the highly reactive singlet oxygen (1O2). However, the link between the presence of electrocatalysts and 1O2 formation in metal-O2 cells is unknown. Here, we show that, compared to pristine carbon black electrodes, a representative selection of electrocatalysts or non-carbon electrodes (noble metal, transition metal compounds) may both slightly reduce or severely increase the 1O2 formation. The individual reaction steps, where the surfaces impact the 1O2 yield are deciphered, showing that 1O2 yield from superoxide disproportionation as well as the decomposition of trace H2O2 are sensitive to catalysts. Transition metal compounds in general are prone to increase 1O2. <br>

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“…Azide could be an interesting quencher for these energy storage systems, as recently demonstrated for both Li and Na-O 2 batteries (Córdoba et al, 2019;Lozano et al, 2020). However, due to the explosive potential and safety concerns, azide should be avoided whenever possible if there is a reasonable alternative.…”

Section: How Singlet Oxygen Can Be Deactivated?mentioning

confidence: 99%

“…Wandt et al demonstrated that this degradation was ascribed to the presence of intermediate species such as the generation of singlet oxygen at charge potentials between 3.55 and 3.75 V (vs. Li + /Li) (Wandt et al, 2016 ). The latest studies on the mechanisms involving the generation of singlet oxygen in Li-O 2 batteries, conclude that the major source of 1 O 2 is the disproportionation (also known as dismutation) of LiO 2 ( Figure 2 , reaction 8) through the following mechanism (Córdoba et al, 2019 ; Mourad et al, 2019 ; Wang and Lu, 2020 ):…”

Section: What Are the Implications For Metal-o 2 Bmentioning

confidence: 99%

Unraveling the Effect of Singlet Oxygen on Metal-O2 Batteries: Strategies Toward Deactivation

Larramendi

Ortiz‐Vitoriano

2020

Front. Chem.

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Aprotic metal-O 2 batteries have attracted the interest of the research community due to their high theoretical energy density that target them as potential energy storage systems for automotive applications. At present, these devices show various practical problems, which hinder the attainment of the high theoretical energy densities. Among the main limitations, we can highlight the irreversible parasitic reactions that lead to premature death of the battery. The degradation processes, mainly related to the electrolyte, lead to the formation of secondary products that accumulate throughout the cycling in the air electrode. This accumulation of predominantly insulating products results in the blocking of active sites, promoting less efficiency in system performance. Recently, it has been discovered that the superoxide intermediate radical anion is involved in the generation of the reactive oxygen singlet species (1 O 2) in metal-O 2 batteries. The presence of singlet oxygen is intimately linked with electrolyte degradation processes and with carbon-electrode corrosion reactions. This review analyzes the nature of singlet oxygen, while clarifying its toxic role in metal-O 2 batteries. Besides, the main mechanisms of deactivation of singlet oxygen are presented, trying to inspire the research community in the development of new molecules capable of mitigating the harmful effects related to this highly reactive species.

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

Cited by 26 publications

References 29 publications

Singlet Oxygen in Lithium−Oxygen Batteries

Singlet Oxygen in Lithium−Oxygen Batteries

Surface and Catalyst Driven Singlet Oxygen Formation in Li-O2 Cells

Unraveling the Effect of Singlet Oxygen on Metal-O2 Batteries: Strategies Toward Deactivation

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