Reactivity of Amide Based Solutions in Lithium–Oxygen Cells

Sharon, Daniel; Hirsberg, Daniel; Afri, Michal; Garsuch, Arnd; Frimer, Aryeh A.; Aurbach, Doron

doi:10.1021/jp506230v

Cited by 61 publications

(70 citation statements)

References 30 publications

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“…[36,37] Experimental results on the stability of amides against nucleophilic attacks,however, are not conclusive. [39,40]…”

Section: The Role Of Oxygen Species In Nucleophilic Attackmentioning

confidence: 99%

“…See Section 2.5 for discussions of the SEI formation and functionality. [31,35] --Ether/polyether -O ,P [20,42,44,51] -O [43] DMSO B, [32] N [30] B, [32] N, [30] P [46] R [19] -Ionic liquid -B [47,48] R [47] -Amide -N [39,40] R [55] -Notes:N:nucleophilic attack;B:acid-base reaction;O:auto-oxidation; P: proton-mediated process;R:r eduction by Li.…”

Section: Corrosion Of Lithium By the Electrolytesmentioning

confidence: 99%

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Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

et al. 2016

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“…[36,37] Experimental results on the stability of amides against nucleophilic attacks,however, are not conclusive. [39,40]…”

Section: The Role Of Oxygen Species In Nucleophilic Attackmentioning

confidence: 99%

Section: Corrosion Of Lithium By the Electrolytesmentioning

confidence: 99%

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

et al. 2016

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“…30 Cells containing LiNO 3 in amide solvents showed poor cycling performance because amide solvents tend to decompose in the presence of oxygen reduction. 31,32 However, one positive feature observed was the low OER overpotential obtained, which was associated with the redox behavior of LiNO 3 byproducts. 32 The use of LiNO 3 in other solvents also showed positive results.…”

Section: ■ Introductionmentioning

confidence: 99%

“…31,32 However, one positive feature observed was the low OER overpotential obtained, which was associated with the redox behavior of LiNO 3 byproducts. 32 The use of LiNO 3 in other solvents also showed positive results. Thus, Kang et al 33 report that LiNO 3 introduced into ether-based solvents decomposes on the carbon surface, forming nitrogen-containing groups that protect the carbon from corrosion at high oxidation potentials.…”

Section: ■ Introductionmentioning

confidence: 99%

Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells

Sharon

Hirsberg

Afri

et al. 2015

ACS Appl. Mater. Interfaces

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139

156

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The development of a successful Li-O2 battery depends to a large extent on the discovery of electrolyte solutions that remain chemically stable through the reduction and oxidation reactions that occur during cell operations. The influence of the electrolyte anions on the behavior of Li-O2 cells was thought to be negligible. However, it has recently been suggested that specific anions can have a dramatic effect on the chemistry of a Li-O2 cell. In the present paper, we describe how LiNO3 in polyether solvents can improve both oxygen reduction (ORR) and oxygen evolution (OER) reactions. In particular, the nitrate anion can enhance the ORR by enabling a mechanism that involves solubilized species like superoxide radicals, which allows for the formation of submicronic Li2O2 particles. Such phenomena were also observed in Li-O2 cells with high donor number solvents, such as dimethyl sulfoxide dimethylformamide (DMF) and dimethylacetamide (DMA). Nevertheless, their instability toward oxygen reduction, lithium metals, and high oxidation potentials renders them less suitable than polyether solvents. In turn, using catalysts like LiI to reduce the OER overpotential might enhance parasitic reactions. We show herein that LiNO3 can serve as an electrolyte and useful redox mediator. NO2(-) ions are formed by the reduction of nitrate ions on the anode. Their oxidation forms NO2, which readily oxidizes to Li2O2. The latter process moves the OER overpotentials down into a potential window suitable for polyether solvent-based cells. Advanced analytical tools, including in situ electrochemical quartz microbalance (EQCM) and ESR plus XPS, HR-SEM, and impedance spectroscopy, were used for the studies reported herein.

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“…This suggests that NMP could be unstable in the presence of LiO 2 − (solv) and this nucleophilic reaction is likely to contribute to the degradation of NMP in the Li-air battery, as observed in some recent experiments. 33,35,38,39 What is even more interesting is that the carbonyl carbon in an amide group is generally considered relatively protected toward nucleophilic attacks among functional groups that contain a carbonyl group. The fact that even this amide carbon is susceptible to nucleophilic attacks by LiO 2 − (solv) suggests that most of the solvents that have carbonyl groups would be expected to demonstrate similar vulnerability.…”

Section: Resultsmentioning

confidence: 99%

Exploring Solvent Stability against Nucleophilic Attack by Solvated LiO₂⁻in an Aprotic Li-O₂Battery

Chau

Chen

et al. 2016

J. Electrochem. Soc.

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Solvent degradation due to reactivity with various oxygen species is one of the most important issues in aprotic Li-O 2 batteries. Recently, a more complete mechanism for discharge in an aprotic Li-air battery has been proposed, which accounts for the formation of solvated peroxides by disproportionation. In the present work, nucleophilic attacks by one of these solvated peroxides, LiO 2 − (solv) on some commonly used solvents in aprotic Li-air batteries, including acetonitrile (MeCN), 1-methyl-2-pyrrolidone (NMP), dimethoxy ethane (DME), and dimethyl sulfoxide (DMSO) have been explored by calculating the reaction and activation free energies using density functional theory (DFT) Active research 1-17 on the aprotic Li-air battery has been drawn by its high theoretical energy and power storage capacities of 11,000 Wh/kg and 3800 mAh/g, respectively.18,19 These values double those of the most advanced lithium ion batteries and close to those of gasoline. However, many challenges 20 must be overcome before a commercially viable battery can be produced. One critical issue is the degradation of solvents during the charge and discharge cycles of the battery. Common solvents in Li-air batteries such as propylene carbonate (PC), ethylene carbonate (EC), and dimethyl carbonate (DMC) have long been shown to degrade during discharge and fail to produce lithium peroxide (Li 2 O 2 ), the desired discharge product in a twoelectron process 21-23 described byBryantsev et al. [24][25][26] attributed this failure to the reactions between these solvents and the superoxide radical ion (O 2 − ) with the latter formed inevitably during discharge in the one-electron reduction of oxygen shown in Equation 2 as

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Reactivity of Amide Based Solutions in Lithium–Oxygen Cells

Cited by 61 publications

References 30 publications

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells

Exploring Solvent Stability against Nucleophilic Attack by Solvated LiO₂⁻in an Aprotic Li-O₂Battery

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Reactivity of Amide Based Solutions in Lithium–Oxygen Cells

Cited by 61 publications

References 30 publications

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Catalytic Behavior of Lithium Nitrate in Li-O2 Cells

Exploring Solvent Stability against Nucleophilic Attack by Solvated LiO2−in an Aprotic Li-O2Battery

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Catalytic Behavior of Lithium Nitrate in Li-O₂ Cells

Exploring Solvent Stability against Nucleophilic Attack by Solvated LiO₂⁻in an Aprotic Li-O₂Battery