Chemical Instability of Dimethyl Sulfoxide in Lithium–Air Batteries

Kwabi, David G.; Batcho, Thomas P.; Amanchukwu, Chibueze V.; Ortiz‐Vitoriano, Nagore; Hammond, Paula T.; Thompson, Carl V.; Shao‐Horn, Yang

doi:10.1021/jz5013824

Cited by 226 publications

(272 citation statements)

References 49 publications

(110 reference statements)

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“…[47][48][49] This argument is supported by increasing computed DG* solv (O 2 À ) with decreasing computed pK a of solvents (in DMSO; Supporting Information, Table S2), and previous findings which established a correlation between solvent AN and DN, and pK a , where solvents with higher Li…”

supporting

confidence: 72%

Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

et al. 2016

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supporting

confidence: 72%

Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

et al. 2016

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“…However, there is tremendous scope in tuning the electrolyte anion in low-DN solvents to obtain high discharge capacities. Given that it should be simpler to identify anions stable to the Li-O 2 cathode electrochemistry than high-DN solvents (36,37), anion selection in combination with low-DN solvents potentially provides a route to avoid the unfavorable capacity/stability trade-off observed in high-DN solvents, such as DMSO (14,15,38,39).…”

Section: Resultsmentioning

confidence: 99%

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity

Burke

Pande

Khetan

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

312

344

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Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O 2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O 2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O 2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using 7 Li NMR and modeling, we confirm that this improvement is a result of enhanced Li + stability in solution, which, in turn, induces solubility of the intermediate to Li 2 O 2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation.donor number | solubility | lithium nitrate | NMR | Li-air battery T he lithium-oxygen (Li-O 2 ) battery has garnered significant research interest in the past 10 y due to its high theoretical specific energy compared with current state-of-the-art lithiumion (Li-ion) batteries (1, 2). Consisting of a lithium anode and an oxygen cathode, the nonaqueous Li-O 2 battery operates via the electrochemical formation and decomposition of lithium peroxide (Li 2 O 2 ). The ideal overall reversible cell reaction is thereforeOne challenge preventing the realization of a modest fraction of the Li-O 2 battery's high theoretical specific energy is that the discharge product, Li 2 O 2 , which is generally insoluble in aprotic organic electrolytes, is an insulator (3-5). As Li 2 O 2 is conformally deposited on the cathode's carbon support during discharge, it electronically passivates the cathode, resulting in practical capacities much smaller than theoretically attainable (6). Recently, two reports described the engineering of electrolytes to circumvent this passivation and improve Li-O 2 battery discharge capacity. Aetukuri et al. suggested that adding ppm quantities of water to a 1,2-dimethoxyethane (DME)-based electrolyte increases the solubility of intermediates during Li 2 O 2 formation (7). This increased solubility allows a reduced oxygen species shuttling mechanism that promotes deposi...

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“…Figure 10. [107] In addition, the decomposition of DMSO and the transformation of Li 2 O 2 into LiOH could be accelerated by adding KO 2 .…”

Section: Dmso Electrolytementioning

confidence: 99%

Section: Amide-based Electrolytementioning

confidence: 99%

Review of Electrolytes in Nonaqueous Lithium–Oxygen Batteries

Guo

Luo

Chen

et al. 2018

Advanced Sustainable Systems

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Based on an inexhaustible and ubiquitous source of oxygen, the lithium-oxygen batteries are currently the subject of much scientific investigation because of their potential for extremely high energy density. The electrocatalytic materials for them have been extensively researched during the past decade. Even though they are a key component in the lithium-oxygen batteries, however, the study of electrolytes is still in its primary stage. Electrolytes have an important influence on the electrochemical performance of lithium-oxygen batteries, especially on their cycling stability and rate capacity. Therefore, it is important to select an ideal electrolyte with excellent stability against attack by reaction intermediates, along with excellent oxygen solubility and diffusivity. In this review, the physicochemical and electrochemical properties of organic electrolytes for lithium-oxygen batteries are discussed and compared. Furthermore, possible research directions are proposed for the development of an ideal electrolyte for enhanced electrochemical performance. Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsGuo, H., Luo, W., Chen, J., Chou, S., Liu, H. & Wang, J. (2018 Figure 1. Unlike the intercalation mechanism of lithium-ion batteries or sodium-ion batteries, the Li-O 2 battery systems employ a dissolution/ deposition reaction with an air electrode that uses oxygen as the cathode electrode during the electrochemical processes. Research on the Li-O 2 battery is complicated by the need for exposure the air cathode to O 2 atmosphere.Many advances have been achieved, which include advances on cathode materials, electrolytes, anode materials, and redox mediators. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Several excellent reviews have been published to summarize recent developments and our current understanding of Li-O 2 batteries, especially with respect to the cathode electrocatalytic materials. [25][26][27][28][29][30][31][32][33][34][35] These reviews have comprehensively discussed the relationship between the structure of electrocatalytic materials and the electrochemical performance of Li-O 2 batteries. There are, however, few reviews focused on the effects of different electrolytes on the electrochemical performance of the Li-O 2 batteries. [36][37][38] For the aqueous Li-O 2 batteries, LiOH is generated or oxidized at the cathode during discharge and charge processes because H 2 O and O 2 are involved in the reactions. In the case of the nonaqueous Li-O 2 batteries, there are two essential processes that determine their electrochemical performance: the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). During the ORR process, the Li 2 O 2 is precipitated as the final discharge product on the air cathode, while during the OER process, Li 2 O 2 is then decomposed and the O 2 is regenerated. Therefore, there are huge differences between aqueous and nonaqueous Li-O 2 batteries. Since the nonaqueous Li-O 2 batteries have dominated ...

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Chemical Instability of Dimethyl Sulfoxide in Lithium–Air Batteries

Cited by 226 publications

References 49 publications

Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity

Review of Electrolytes in Nonaqueous Lithium–Oxygen Batteries

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Chemical Instability of Dimethyl Sulfoxide in Lithium–Air Batteries

Cited by 226 publications

References 49 publications

Experimental and Computational Analysis of the Solvent‐Dependent O2/Li+‐O2− Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Experimental and Computational Analysis of the Solvent‐Dependent O2/Li+‐O2− Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O 2 battery capacity

Review of Electrolytes in Nonaqueous Lithium–Oxygen Batteries

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Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Experimental and Computational Analysis of the Solvent‐Dependent O₂/Li⁺‐O₂⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O ₂ battery capacity