Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes

Zhang, Zhengcheng; Assary, Rajeev S.; Du, Peng; Wang, Hsien Hau; Sun, Yang Kook; Qin, Yan; Lau, Kah Chun; Greeley, Jeffrey; Redfern, Paul C.; Iddir, Hakim; Curtiss, Larry A.; Amine, Khalil

doi:10.1021/jp2087412

Cited by 167 publications

(189 citation statements)

References 37 publications

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“…The slightly higher yields indicate that the relatively high surface area of the Li 2 O 2 film that grows on the electrode in the absence of DBBQ leads to more decomposition of the electrolyte solution than is the case for the large particles in solution. It has also been suggested that LiO 2 is responsible for solvent decomposition on discharge 26,41,42 and, as discussed below, our analysis points to a mechanism that avoids this reactive intermediate. Attempts to charge the cells after discharge proved fruitless (see Supplementary Fig.…”

Section: Cyclic Voltammetry Studies With Dbbqsupporting

confidence: 68%

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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Section: Cyclic Voltammetry Studies With Dbbqsupporting

confidence: 68%

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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“…The cathode may contain a catalyst in some form to promote the discharge reaction. It has been found that a variety of factors dictate the nature of electrochemical reactions in Li-air cells including the nature of the catalyst, the catalyst distribution on the porous cathode, the pore volume of the cathode and the type of organic electrolyte used [3][4][5][6][7][8][9][10] .…”

mentioning

confidence: 99%

“…Some of the early work on Li-O 2 batteries was based on carbonate electrolytes including catalysts such as aMnO 2 , Co 3 O 4 , Mn 3 O 4 and PtAu [11][12][13][14][15] . However, carbonate electrolytes were found to decompose in Li-O 2 batteries 1,16,17 and consequently researchers turned to ether-based electrolytes, which have greater stability 8,11,18 . In a dimethoxyethane-based electrolyte, McCloskey et al 19 investigated the electrocatalytic role of Au, Pt and MnO 2 nanoparticles and found that none of these nanoparticles performs better than just a carbon surface.…”

mentioning

confidence: 99%

A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries

et al. 2013

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The lithium-oxygen battery, of much interest because of its very high-energy density, presents many challenges, one of which is a high-charge overpotential that results in large inefficiencies. Here we report a cathode architecture based on nanoscale components that results in a dramatic reduction in charge overpotential to B0.2 V. The cathode utilizes atomic layer deposition of palladium nanoparticles on a carbon surface with an alumina coating for passivation of carbon defect sites. The low charge potential is enabled by the combination of palladium nanoparticles attached to the carbon cathode surface, a nanocrystalline form of lithium peroxide with grain boundaries, and the alumina coating preventing electrolyte decomposition on carbon. High-resolution transmission electron microscopy provides evidence for the nanocrystalline form of lithium peroxide. The new cathode material architecture provides the basis for future development of lithium-oxygen cathode materials that can be used to improve the efficiency and to extend cycle life.

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“…These studies included different carbons [6][7][8] and polycrystalline metal surfaces such as nanoporous gold 9,10 , all of which have a variety of active sites. Other studies have reported supported nanoparticles as electrocatalysts in Li-O 2 cells [11][12][13][14][15] . In addition, during the deposition process of nanoparticles it is possible that small clusters may also be present that are acting as electrocatalysts as has been found in surface reactions involving gold clusters 16 .…”

mentioning

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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Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes

Cited by 167 publications

References 37 publications

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

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

A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries

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

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