Implications of CO<sub>2</sub> Contamination in Rechargeable Nonaqueous Li–O<sub>2</sub> Batteries

Gowda, Sanketh R.; Brunet, Annie; Wallraff, Gregory M.; McCloskey, Bryan D.

doi:10.1021/jz301902h

Cited by 259 publications

(284 citation statements)

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“…The onset of CO 2 evolution at 3.8 V is in accordance with the equilibrium potential of Reaction 1 ( E °=3.82 V vs. Li/Li + ) 4c, 6. Consistent with numerous studies, O 2 was not detected throughout charging 4c,4g,4h, 5b. H 2 and CO evolution is observed above 4.2 V during the anodic scan of the Li 2 CO 3 ‐packed electrodes, but no gas evolution is observed below 4.5 V from blank carbon black electrodes (Figure S3).…”

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confidence: 90%

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

et al. 2018

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Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e−+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3.

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confidence: 90%

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

et al. 2018

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“…[41] They claimed that Li 2 O 2 formed via a 2e − /O 2 process is the main discharge product in more stable solvents such as DME, regardless of whether CO 2 is present or not. However, results indicated that CO 2 in the feed gas can spontaneously react with Li 2 O 2 to form the discharge product Li 2 CO 3 , which results in an increase in charging potential, thereby dramatically reducing the rechargeability of the Li-O 2 battery (Figure 2).…”

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confidence: 99%

Progress and Future Perspectives on Li(Na)–CO₂ Batteries

Cai

Chou

2018

Advanced Sustainable Systems

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Li(Na)-CO2 batteries are attracting significant research attention due to contemporary energy and environmental issues. Li(Na)-CO2 batteries make possible the utilization of CO2 and open up a new avenue for energy conver-sion and storage. Research on this system is currently in its infancy, and its development is still faced with many challenges in terms of high charge potential, weak rate capability, and poor cyclability. Moreover, the reaction mechanism in the battery is still unclear and hard to determine, due to the generation of carbon along with metal carbonates on the cathode. In this review, the authors present the fundamentals and the latest progress related to Li(Na)-CO2 research. Detailed discussions are provided on the electrochemical reactions on cathode, cathode materials, and electrolytes. Current challenges and future perspectives on Li(Na)-CO2 batteries are also proposed Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsCai, F., Hu, Z. & Chou, S. (2018 [17][18][19][20][21][22][23][24][25][26][27][28] As a new battery technology, metal-air batteries still face a number of problems, such as poor cycling performance, decomposition of electrolyte, high overpotentials etc. [29][30][31] It is well known that metal-air batteries with an open cell structure can generate power by the electrochemical reaction between metal and oxygen from the atmosphere. Using ambient air as the cathode for metal-air batteries, however, brings even more problematic molecules into the battery system. For example, moisture and CO 2 from the air easily react with the metal and discharge products to form insulating metal hydroxides and metal carbonates at the cathode, which can induce low energy efficiency and poor cycling stability. [32] Thus, most metal-air batteries in laboratories today run in a pure oxygen environment instead of ambient air.Although the concentration of CO 2 is low in ambient air (only 0.03 vol%), [33] CO 2 is known to be more soluble in organic electrolytes than O 2 (≈50 times higher than O 2 ), [34] resulting in the high possibility of CO 2 participation in battery reactions. Considering the influence of CO 2 on the operation of metalair batteries, researchers have focused on metal-CO 2 batteries that utilize an O 2 /CO 2 mixture or pure CO 2 as the reactant gas in the cathode, providing us with a new platform for electrical energy generation and CO 2 conversion and utilization. [35][36][37] At present, Li(Na)-CO 2 batteries have attracted most attention in relation to the development of primary metal-O 2 /CO 2 batteries to achieve rechargeable metal-CO 2 batteries.[38-50] The Li(Na)-CO 2 battery exhibits a high theoretical energy density of 1876 Wh kg −1 (1.13 kWh kg −1 for Na) based on the reaction of 4Li(Na) + 3CO 2 ↔ 2Li(Na) 2 CO 3 + C. [36,44] The operation of a rechargeable Li(Na)-CO 2 battery, however, is faced with the critical challenges of the poor round-trip efficiency and the decomposition of electrolyte caused by high charge overpotential, as well as o...

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“…Hence, a more reasonable specific energy of 3.5 kWh/kg is obtained assuming lithium peroxide (Li 2 O 2 ) 2 as the sole discharge product. In practice Li-air batteries suffer from rapid capacity fading due to several obstacles such as poisoning the lithium electrode with CO 2 , 3 moisture and the instability of organic electrolyte used today against superoxide ion radical (O 2 -• ). 4 One main challenge to overcome in the attempt to develop a reversible Li-O 2 batteries with high capacity is the selection of an appropriate non-aqueous electrolyte which is characterized by high stability in the presence of lithium oxide species and a wide potential window.…”

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confidence: 99%

Quantitative Study for Oxygen Reduction and Evolution in Aprotic Organic Electrolytes at Gas Diffusion Electrodes by DEMS

Bondue

Abd-El-Latif

Hegemann

et al. 2015

J. Electrochem. Soc.

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Cyclic voltammetry and differential electrochemical mass spectrometry (DEMS) have been combined to study the cycling performance of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at a gold electrode in non-aqueous dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) based LiClO 4 and N(Bu) 4 ClO 4 containing electrolytes. An Au-sputtered Teflon membrane (with a thickness of Au of only 50 nm resulting in an extremely short pore length on the electrolyte side) has been used as a model for a gas diffusion electrode (GDE) in this study: The oxygen molecules diffuse through a membrane from the gas side and are reduced at Au on the electrolyte side. The redox couple O 2 −• /O 2 is the predominant reaction during ORR in N(Bu) 4 ClO 4 based electrolytes whereas the calculated number of electron transferred is one. In presence of Li-ions, the average number of electrons transferred is 2 during oxygen reduction, which indicates the formation and oxidation of peroxide during ORR and OER respectively. The mass spectrometric cyclic voltammograms (MSCVs) data show that the maximum true coulombic efficiency of OER/ORR in DMSO and NMP is about 60% and 25%, respectively, with the evolution of CO 2 in NMP at 0.1 V (vs. Ag + /Ag) due to the decomposition of the electrolyte. One of today's challenges is the development of an energy storage system that can provide both high capacity and good cycling performance. Secondary lithium-air batteries are promising candidates as they provide a high theoretical capacity. However in practice, cycling performance is bad. The key step in discharging these batteries is the reduction of oxygen present in air. So far the oxygen reduction reaction has been investigated thoroughly in aqueous media, but only little fundamental research has been done in non-aqueous solvents.The first non-aqueous lithium-air battery was introduced in 1996 by Abraham and Jiang 1 as an alternative energy storage system for future applications. The specific energy of a Li-air battery amounts to 5.21 kWh/kg (including the weight of O 2 ), based on the assumption that Li fully reacts with O 2 to form Li 2 O.1 However, in practice the route to Li 2 O has proven irreversible. Hence, a more reasonable specific energy of 3.5 kWh/kg is obtained assuming lithium peroxide (Li 2 O 2 ) 2 as the sole discharge product. In practice Li-air batteries suffer from rapid capacity fading due to several obstacles such as poisoning the lithium electrode with CO 2 , 3 moisture and the instability of organic electrolyte used today against superoxide ion radical (O 2 -• ). 4 One main challenge to overcome in the attempt to develop a reversible Li-O 2 batteries with high capacity is the selection of an appropriate non-aqueous electrolyte which is characterized by high stability in the presence of lithium oxide species and a wide potential window. There are further requirements for the electrolyte in battery applications, such as low flammability, low vapor pressure and a large temperature range in which it is p...

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Implications of CO₂ Contamination in Rechargeable Nonaqueous Li–O₂ Batteries

Cited by 259 publications

References 23 publications

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Progress and Future Perspectives on Li(Na)–CO₂ Batteries

Quantitative Study for Oxygen Reduction and Evolution in Aprotic Organic Electrolytes at Gas Diffusion Electrodes by DEMS

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Implications of CO2 Contamination in Rechargeable Nonaqueous Li–O2 Batteries

Cited by 259 publications

References 23 publications

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Progress and Future Perspectives on Li(Na)–CO2 Batteries

Quantitative Study for Oxygen Reduction and Evolution in Aprotic Organic Electrolytes at Gas Diffusion Electrodes by DEMS

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Product

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Implications of CO₂ Contamination in Rechargeable Nonaqueous Li–O₂ Batteries

Progress and Future Perspectives on Li(Na)–CO₂ Batteries