Materials challenges in rechargeable lithium-air batteries

Kwabi, David G.; Ortiz‐Vitoriano, Nagore; Freunberger, Stefan; Chen, Yuhui; Imanishi, N.; Bruce, Peter G.; Shao‐Horn, Yang

doi:10.1557/mrs.2014.87

Cited by 140 publications

(136 citation statements)

References 82 publications

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“…Among the few alternatives is the lithium−air battery, which has high theoretical specific energy density (11.7 kW·h·kg −1 ), 4−7 with a practical specific energy density close to 3.5 kW·h·kg −1 being reported. 8 These batteries have been studied extensively since the report on the first nonaqueous secondary battery. 9 Catalysts in the positive electrode can enhance the oxygen reduction reaction (ORR) rate to deliver and store energy efficiently.…”

Section: ■ Introductionmentioning

confidence: 99%

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

et al. 2014

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The high theoretical energy density of lithium−oxygen batteries brings the promise of higher performance than existing batteries, but several technological problems must be addressed before actual applications are made possible. Among the difficulties to be faced is the slow oxygen reduction reaction (ORR), which requires a suitable choice of catalysts and electrolytic solution. This can only be achieved if the kinetics and mechanism of this reaction are known in detail. In this study, we determined the rate constants for each elementary step of ORR for a platinum electrode in 0.1 mol•L −1 LiClO 4 /1,2-dimethoxyethane (DME), using a kinetic model in the frequency domain. We found that the energy storage capacity of lithium−air batteries can be increased by converting a large amount of lithium superoxide into lithium peroxide during the electrochemical step in comparison with chemical disproportionation. The mechanisms for ORR were supported by data from an electrochemical quartz crystal microbalance (EQCM): ORR could be distinguished from parasitic reactions induced by solvent degradation, and agglomerates of Li x O 2 (1 ≤ x ≤ 2) were adsorbed on the electrode. The rate-limiting step for ORR was the electron transfer to the oxygen molecules strongly adsorbed onto platinum sites, particularly as a large amount of reaction product (Li 2 O 2 ) adsorbed onto the electrode. Even though Pt sheets are likely to be impracticable for real applications due to their low surface area, they were useful in making it possible to determine the kinetics of ORR steps. This can now be employed to devise more involved electrodes, such as those containing dispersed Pt nanoparticles.

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Section: ■ Introductionmentioning

confidence: 99%

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

et al. 2014

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“…Activating O 2 [1][2][3][4] is central to transforming energy storage by providing high gravimetric energy in devices such as rechargeable Li-O 2 [5,6] and Na-O 2 batteries [7] and reversible fuel cells. [8] Non-aqueous Li-O 2 batteries operate by reducing molecular O 2 in the presence of Li + to form Li 2 O 2 at the positive electrode on discharge and releasing O 2 by oxidizing Li 2 O 2 on charge.…”

mentioning

confidence: 99%

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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“…1 Consequently, these batteries are considered one of the most promising candidates for high energy storage devices such as electric vehicles (EVs) or hybrid electric vehicles (HEVs), which have become of special interest due to the fossil fuel depletion and the demand of a cheaper, nontoxic and environmentally friendly energetic model. This technology is still however in its early stages and some challenges need to be overcome in order to make them commercially available.…”

mentioning

confidence: 99%

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

Landa‐Medrano

Pinedo

Larramendi

et al. 2015

J. Electrochem. Soc.

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The performance of Li-O 2 batteries is typically evaluated by specific capacity and cyclability in order to facilitate quantitative comparison in literature. The accuracy of such comparison is limited, however, due to the wide range of factors which control the reported specific capacities. These comparisons are not always fair as some factors, which can highly influence the obtained specific capacities, are often neglected. A rigorous and systematic study has been conducted in order to identify the isolated effect of diverse parameters on the performance of these promising batteries. The analysis of cells with different carbon contents reveals that the discharge reactions do not necessarily take place throughout the electrode mass, but instead occur preferentially in closest proximity to the oxygen gas-electrolyte interface. The effective activity of the cathode material is therefore reduced as distance from this interface increases. This work demonstrates that the lack of standardized measurement protocols hinders the rapid development of this technology due to the difficulties inherent in the direct comparison of cells with wide-ranging measurement conditions. In addition, it has been demonstrated that both the employed carbon loading and current rate critically affect cycling lifetime. Lithium-oxygen (Li-O 2 ) rechargeable batteries with organic electrolytes have recently received extraordinary attention due to their potential to provide high gravimetric energies (∼3500 Wh/kg based on the cell reaction, 2Li + O 2 ↔ Li 2 O 2 ; 2.96 V vs Li/Li + ). 1 Consequently, these batteries are considered one of the most promising candidates for high energy storage devices such as electric vehicles (EVs) or hybrid electric vehicles (HEVs), which have become of special interest due to the fossil fuel depletion and the demand of a cheaper, nontoxic and environmentally friendly energetic model. This technology is still however in its early stages and some challenges need to be overcome in order to make them commercially available.2-12 Although existing lithium-ion technology was initially adopted in order to start investigating these relatively new batteries, numerous problems reveal that this is not always suitable. For example, the carbonate based solvents, commonly used in Li-ion batteries, 13 were not appropriate for Li-O 2 batteries because of their susceptibility to nucleophilic attack by reduced O 2 − species.10,14-17Li-O 2 batteries usually consist of a lithium foil anode, a lithium salt dissolved in an organic solvent as electrolyte and a porous carbonbased cathode. During the discharge metallic lithium anode releases lithium ions (Li + ) to the electrolyte, while electrons are transported to the cathode through an external circuit.Meanwhile, oxygen molecules are reduced (oxygen reduction reaction, (ORR)) at the cathode.18 The global reaction taking place in the battery is:Solubility and diffusion rate of oxygen in the electrolyte play key roles in determining battery performance. 21,22 Zhang et al. proposed a liqu...

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Materials challenges in rechargeable lithium-air batteries

Abstract: Abstract

Cited by 140 publications

References 82 publications

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

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

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries

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Materials challenges in rechargeable lithium-air batteries

Abstract: Abstract

Cited by 140 publications

References 82 publications

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

Investigating the Kinetic Mechanisms of the Oxygen Reduction Reaction in a Nonaqueous Solvent

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

Monitoring the Location of Cathode-Reactions in Li-O2Batteries

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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

Monitoring the Location of Cathode-Reactions in Li-O₂Batteries