Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst

Lim, Hee‐Dae; Song, Hyelynn; Kim, Jin-Soo; Gwon, Hyeokjo; Bae, Youngjoon; Park, Kyu Young; Hong, Jihyun; Kim, Haegyeom; Kim, Taewoo; Kim, Yong Hyup; Lepró, Xavier; Ovalle‐Robles, Raquel; Baughman, Ray H.; Kang, Kisuk

doi:10.1002/anie.201400711

Cited by 424 publications

(323 citation statements)

References 40 publications

(48 reference statements)

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“…For dye-sensitized TiO 2 solar cells, the triiodide/iodide (I 3 À /I À ) redox couple is a benchmark electrolyte for the dye regeneration 24 . Despite being mentioned in a patent 12 and a very recent publication 14 , not much attention has been placed on utilizing I 3 À /I À redox couple for non-aqueous Li-O 2 batteries. Therefore, we started with investigating the I 3 À /I À couple as a redox shuttle for Li-O 2 batteries.…”

Section: Resultsmentioning

confidence: 99%

“…This leads to a severe charging overpotential issue, which causes not only a very low battery round-trip efficiency, but also the decompositions of the oxygen electrode and electrolyte 3,4,7,9 . Recently, redox shuttles, such as tetrathiafulvalene (TTF þ /TTF), have been introduced in the battery electrolyte to address this poor charge transport issue [10][11][12][13][14] . During the charging process, the reduced form of the redox shuttle, M red , is first converted to M ox on the oxygen electrode, which in turn oxidizes the Li 2 O 2 .…”

mentioning

confidence: 99%

“…During the charging process, the reduced form of the redox shuttle, M red , is first converted to M ox on the oxygen electrode, which in turn oxidizes the Li 2 O 2 . By efficiently shuttling charges between Li 2 O 2 particles and the oxygen electrode surface, it facilitates the oxidation of Li 2 O 2 and therefore reduces the overpotential 13,14 .…”

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confidence: 99%

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Integrating a redox-coupled dye-sensitized photoelectrode into a lithium–oxygen battery for photoassisted charging

et al. 2014

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With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Integrating a redox-coupled dye-sensitized photoelectrode into a lithium–oxygen battery for photoassisted charging

et al. 2014

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“…1,2 An efficient electrocatalyst should be bifunctional and robust in nature. A bifunctional electrocatalyst catalyzes both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) during the battery discharge-charge process.…”

Section: Introductionmentioning

confidence: 99%

Hierarchical urchin-shaped α-MnO2 on graphene-coated carbon microfibers: a binder-free electrode for rechargeable aqueous Na–air battery

et al. 2016

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With the increasing demand of cost-effective and high-energy devices, sodium-air (Na-air) batteries have attracted immense interest due to the natural abundance of sodium in contrast to lithium. In particular, an aqueous Na-air battery has fundamental advantage over non-aqueous batteries due to the formation of highly water-soluble discharge product, which improve the overall performance of the system in terms of energy density, cyclic stability and round-trip efficiency. Despite these advantages, the rechargeability of aqueous Na-air batteries has not yet been demonstrated when using non-precious metal catalysts. In this work, we rationally synthesized a binder-free and robust electrode by directly growing urchin-shaped MnO 2 nanowires on porous reduced graphene oxide-coated carbon microfiber (MGC) mats and fabricated an aqueous Na-air cell using the MGC as an air electrode to demonstrate the rechargeability of an aqueous Na-air battery. The fabricated aqueous Na-air cell exhibited excellent rechargeability and rate capability with a low overpotential gap (0.7 V) and high round-trip efficiency (81%). We believe that our approach opens a new avenue for synthesizing robust and binder-free electrodes that can be utilized to build not only metal-air batteries but also other energy systems such as supercapacitors, metal-ion batteries and fuel cells.

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“…This is to be expected because the Li 2 O 2 is not well connected to the electrode surface and therefore direct electrochemical oxidation will be difficult. Therefore, especially in the presence of a reduction-mediated discharge, it will be necessary to employ an oxidation mediator to charge the cell, as described previously 36,[43][44][45] .…”

Section: Cyclic Voltammetry Studies With Dbbqmentioning

confidence: 99%

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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Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst

Cited by 424 publications

References 40 publications

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium–oxygen battery for photoassisted charging

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium–oxygen battery for photoassisted charging

Hierarchical urchin-shaped α-MnO2 on graphene-coated carbon microfibers: a binder-free electrode for rechargeable aqueous Na–air battery

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

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