Indigo carmine: An organic crystal as a positive-electrode material for rechargeable sodium batteries

Yao, Masaru; Kuratani, Kentaro; Kojima, Toshikatsu; Takeichi, Nobuhiko; Senoh, Hiroshi; Kiyobayashi, Tetsu

doi:10.1038/srep03650

Cited by 117 publications

(108 citation statements)

References 39 publications

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“…The potential profiles of the DMBQ electrode during the first cycle are shown in Figure 5. The first discharge curves show two potential plateaus that we often observe for quinone-based electrodes in Li, 8 Na 20 and Mg 7 systems. For all of these solutions, the plateaus are located at around 0.8 and 0.4 V vs. Mg quasi , which are about 2 V lower than those in the Li system.…”

Section: Resultsmentioning

confidence: 54%

Sulfone-Based Electrolyte Solutions for Rechargeable Magnesium Batteries Using 2,5-Dimethoxy-1,4-benzoquinone Positive Electrode

Senoh

Sakaebe

Sano

et al. 2014

J. Electrochem. Soc.

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We examined three sulfone-based electrolyte solutions for use in rechargeable magnesium batteries; i.e., sulfolane (SL), ethyl-i-propyl sulfone (EiPS) and di-n-propyl sulfone (DnPS), in which was dissolved 0.5 mol L −1 magnesium bis(trifluoromethanesulfonyl)amide (Mg(TFSA) 2 ). The specific conductivities of these sulfone-based Mg-electrolyte solutions were 1-2 mS cm −1 at 30 • C. These electrolyte solutions were thermally stable < 250 • C, and electrochemically stable < 2 V vs. Mg reference electrode (Mg wire). In these electrolyte solutions, an organic positive electrode made of 2,5-dimethoxy-1,4-benzoquinone (DMBQ) underwent reversible charge-discharge reactions. The reduction-oxidation current of the metallic Mg negative electrode was observed. A two-electrode cell composed of Mg|Mg(TFSA) 2 /SL|DMBQ endured more than 50 charge-discharge cycles at 30 • Rechargeable magnesium batteries may be an option for replacing the rechargeable lithium batteries because magnesium is much more abundant in the earth's crust and is more widely distributed than lithium. The fact that metallic Mg is less reactive toward ambient water and oxygen than Li may lead to a safer battery. In addition, a volumetric energy density of Mg should be greater than that of metallic Li.To achieve rechargeable magnesium batteries, it is important to consider the combination of the electrolyte and the positive electrode with the Mg negative electrode.1-3 Some solutions of Grignard reagents (RMgX; R = alkyl, X = halogen) are known to function as an electrolyte, in which metallic Mg is electrochemically and reversibly deposited on and dissolved from the negative electrode. 4 However, Grignard reagents are not stable at the high electrochemical potentials required for the positive electrode. 5 Recently, Nakayama et al. 6 revealed that, for Al electrolyte systems, certain sulfones (RR´SO 2 ) can be used as a solvent that endures high potentials. Thus, in the present study, we investigated three sulfones for use as a solvent to dissolve the Mg solute in rechargeable magnesium batteries; viz., sulfolane (SL), ethyl-i-propyl sulfone (EiPS) and di-n-propyl sulfone (DnPS). As the Mg electrolyte, we used magnesium bis(trifluoromethanesulfonyl)amide (Mg(TFSA) 2 ) because it can tolerate a high potential and the large TFSA anion, a soft Lewis base, should facilitate its dissociation from the Mg 2+ cation. In a Mg electrolyte solution, Mg(ClO 4 ) 2 /GBL, in a threeelectrode cell, we previously investigated the potential capability of 2,5-dimethoxy-1,4-benzoquinone (DMBQ), 7 which works as a positive-electrode active material in the lithium system. 8 In Mg(ClO 4 ) 2 /GBL, however, we found that no reversible Mg deposition/dissolution occurred. The objectives of the present study were to determine the fundamental physical properties of these sulfone electrolyte solutions, e.g., the viscosity, conductivity, potential window, etc., and to demonstrate the battery properties of a full-cell, Mg|Mg(TFSA) 2 /sulfone|DMBQ, to shed light on the possibilities and probl...

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Section: Resultsmentioning

confidence: 54%

Sulfone-Based Electrolyte Solutions for Rechargeable Magnesium Batteries Using 2,5-Dimethoxy-1,4-benzoquinone Positive Electrode

Senoh

Sakaebe

Sano

et al. 2014

J. Electrochem. Soc.

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“…The limited cyclability could be attributable to the non-optimized Na electrolytes of the cell and the large strain of the electrode materials during the insertion of large sodium ions, which may induce the isolation of the active materials from the electrodes. While further studies are required, the sodium-organic battery system is promising for sustainable energy storage systems, since it is based on abundant sodium elements on earth and does not contain transition metals [38][39][40] . The utilization of diazabutadiene redox cycling should provide potential opportunities for sodium-organic battery systems.…”

Section: Resultsmentioning

confidence: 99%

Biologically inspired pteridine redox centres for rechargeable batteries

et al. 2014

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The use of biologically occurring redox centres holds a great potential in designing sustainable energy storage systems. Yet, to become practically feasible, it is critical to explore optimization strategies of biological redox compounds, along with in-depth studies regarding their underlying energy storage mechanisms. Here we report a molecular simplification strategy to tailor the redox unit of pteridine derivatives, which are essential components of ubiquitous electron transfer proteins in nature. We first apply pteridine systems of alloxazinic structure in lithium/sodium rechargeable batteries and unveil their reversible tautomerism during energy storage. Through the molecular tailoring, the pteridine electrodes can show outstanding performance, delivering 533 Wh kg À 1 within 1 h and 348 Wh kg À 1 within 1 min, as well as high cyclability retaining 96% of the initial capacity after 500 cycles at 10 A g À 1 . Our strategy combined with experimental and theoretical studies suggests guidance for the rational design of organic redox centres.

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“…2e4 Recently, indigos and functionalized indigos were applied for optoelectronic devices, such as field effect transistors, 5e7 solar cells, 8,9 sensors, 10,11 and electrodes for ion batteries. 12,13 In particular, Pitayatanakul et al, reported on the halogen or phenyl group functionalized indigos for organic semiconductors. In this series of compounds, the indigos showed a herring-bone like structure for the halogen substitution derivatives, whereas a brickwork arrangement of the crystal structure was observed in the case of phenyl-derivatives because of pep interactions arising from the functionalization substitution at 5-position.…”

Section: Introductionmentioning

confidence: 98%