Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge

Adams, Brian D.; Radtke, C.; Black, Robert W.; Trudeau, Michel; Zaghib, Karim; Nazar, Linda F.

doi:10.1039/c3ee40697k

Cited by 618 publications

(748 citation statements)

References 33 publications

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“…The Ag 9 toroids are smaller than the Ag 15 toroids (B500 nm versus B1,000 nm) with the same discharge capacity. Toroids have been found in the discharge product by others in Li-O 2 cells [31][32][33][34] . The X-ray diffraction (XRD) patterns in Fig.…”

Section: Resultsmentioning

confidence: 99%

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

et al. 2014

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Lithium-oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium-oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. Here we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium-oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. This dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. The results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium-oxygen cells.

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Section: Resultsmentioning

confidence: 99%

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

et al. 2014

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“…[11][12][13][14] [14,15] A number of studies have attributed the formation of large Li 2 O 2 particles and high discharge capacities observed at low rates (< 10 mA cm À2 in ethers [16,17] ), to high availability of soluble Li + -O 2 À . Abraham and co-workers [13,14,18] have suggested that the stability of Li + -O 2 À increases with solvent donor number (DN), which is a measure of the solvation enthalpy of the Lewis acid SbCl 5 in a given solvent .…”

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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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“…In the absence of DBBQ, reduction of O 2 to Li 2 O 2 proceeds via the LiO 2 intermediate 15,16,[18][19][20][21] , and it is the need to reach the potential for formation of LiO 2 that pins the O 2 reduction at a potential (discharge plateau in a Li-O 2 cell) significantly negative of the standard potential for Li 2 O 2 formation, 2.96 V (Fig. 1).…”

Section: The Mechanism Of O 2 Reduction In the Presence Of Dbbqmentioning

confidence: 99%

“…In contrast, if Li 2 O 2 can be induced to grow in the electrolyte solution then high discharge capacities at relatively high rates and avoiding early cell death is possible 15 . It is clearly important to operate a Li-O 2 battery in which Li 2 O 2 grows in solution.A number of groups have elucidated the mechanism of O 2 reduction to Li 2 O 2 on discharge 15,16,[18][19][20][21] . The reduction proceeds through the following general steps: 22,[27][28][29][30] .…”

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confidence: 99%

“…The significance of the present work is that if such stable solvents can be identified then DBBQ provides a route to solution growth of Li 2 O 2 and hence potentially high rates, high capacities and sustained cycling, avoiding early cell death. 15,16,21 , it is necessary to carry out the reduction of O 2 to Li 2 O 2 in solution at a higher potential than the surface reaction, which also has the advantage of increasing the cell discharge potential closer to its thermodynamic potential of 2.96 V (reducing the overpotential). To achieve this, molecules with a redox potential higher than the potential at which O 2 is reduced (discharge plateau in a Li-O 2 cell) are required.…”

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Erratum: Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions

Gao¹,

Chen²,

Johnson³

et al. 2016

Nature Mater

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On discharge, the Li-O 2 battery can form a Li 2 O 2 film on the cathode surface, leading to low capacities, low rates and early cell death, or it can form Li 2 O 2 particles in solution, leading to high capacities at relatively high rates and avoiding early cell death. Achieving discharge in solution is important and may be encouraged by the use of high donor or acceptor number solvents or salts that dissolve the T he high theoretical specific energy of the rechargeable Li-O 2 battery has generated intense interest in the possibility of a practical device that could deliver energy storage significantly in excess of today's lithium-ion batteries 1-9 . However, major challenges hinder the development of such a technology 1-6,10-14 . Typically a Li-O 2 battery is composed of a lithium metal anode separated by an aprotic electrolyte solution from a porous O 2 cathode. The reaction at the cathode involves, on discharge, the reduction of O 2 to form Li 2 O 2 , with oxidation of the latter on charge. Growth of Li 2 O 2 on the cathode surface leads to low capacities, poor rates and early cell death [15][16][17] . In contrast, if Li 2 O 2 can be induced to grow in the electrolyte solution then high discharge capacities at relatively high rates and avoiding early cell death is possible 15 . It is clearly important to operate a Li-O 2 battery in which Li 2 O 2 grows in solution.A number of groups have elucidated the mechanism of O 2 reduction to Li 2 O 2 on discharge 15,16,[18][19][20][21] . The reduction proceeds through the following general steps: 22,[27][28][29][30] . High donor number salts have been shown to increase the capacity fourfold and reduce the discharge overpotential by ∼30-50 mV over low donor number salts 22 . Viologens 27,28 , phthalocyanines 29 and quinones 30 have been investigated as possible soluble reduction catalysts. Although the studies of such catalysts are important, in most cases there is little or no direct evidence demonstrating that they promote formation of Li 2 O 2 in solution and not on the electrode surface because they rely on electrochemical measurements alone. Yet past work on Li-O 2 batteries has shown how essential it is to provide more than electrochemical evidence in this field 31 . In some cases, soluble catalysts show an increase in discharge voltage (lower overpotential) as small as, for example, 40 mV (refs 28,29), which is very unlikely to be sufficient to shut off the direct reduction of O 2 to Li 2 O 2 , essential to stop detrimental Li 2 O 2 film formation. Also, none of the previous studies in low donor number solvents exhibited a significant increase in capacity on discharge at a relatively high rate, which is important for a successful Li-O 2 battery.Here we demonstrate that addition of DBBQ (2,5-di-tert-butyl-1,4-benzoquinone) to a weakly solvating (low donor number) electrolyte solution, LiTFSI in ether 22 , promotes O 2 reduction to Li 2 O 2 in solution while halving the discharge overpotential (increasing the discharge potential), suppressing the growth of a Li 2...

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Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge

Cited by 618 publications

References 33 publications

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

Effect of the size-selective silver clusters on lithium peroxide morphology in 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

Erratum: Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions

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Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge

Cited by 618 publications

References 33 publications

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

Effect of the size-selective silver clusters on lithium peroxide morphology in 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

Erratum: Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions

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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