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Ionic transport in highly concentrated lithium bis(fluorosulfonyl)amide electrolytes with keto ester solvents: structural implications for ion hopping conduction in liquid electrolytes
http://hdl.handle.net/10131/00012480
http://hdl.handle.net/10131/00012480513cf5c1-9b08-4a9f-9688-99561718a805
名前 / ファイル | ライセンス | アクション |
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(2) Kondou_PCCP_21_5097.pdf (2.5 MB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2019-05-21 | |||||
タイトル | ||||||
タイトル | Ionic transport in highly concentrated lithium bis(fluorosulfonyl)amide electrolytes with keto ester solvents: structural implications for ion hopping conduction in liquid electrolytes | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者 |
Kondou, Shinji
× Kondou, Shinji× Thomas, Morgan L.× Mandai, Toshihiko× Ueno, Kazuhide× Dokko, Kaoru× Watanabe, Masayoshi |
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著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
著者所属 | ||||||
Department of Chemistry and Biological Science Studies in Chemistry, Iwate University | ||||||
著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | Recent studies have suggested that a Li ion hopping or ligand- or anion-exchange mechanism is largely involved in Li ion conduction of highly concentrated liquid electrolytes. To understand the determining factors for the Li ion hopping/exchange dominant conduction in such liquid systems, ionic diffusion behavior and Li ion coordination structures of concentrated liquid electrolytes composed of lithium bis(fluorosulfonyl)amide (Li[FSA]) and keto ester solvents with two carbonyl coordinating sites of increasing intramolecular distance (methyl pyruvate (MP), methyl acetoacetate (MA), and methyl levulinate (ML)) were studied. Diffusivity measurements of MP- and MA-based concentrated electrolytes showed faster Li ion diffusion than the solvent and FSA anion, demonstrating that Li ion diffusion was dominated by the Li ion hopping/exchange mechanism. A solvent-bridged, chain-like Li ion coordination structure and highly aggregated ion pairs (AGGs) or ionic clusters e.g. Li_x[FSA]_y~(y−x)− forming in the electrolytes were shown to contribute to Li ion hopping conduction. By contrast, ML, with greater intramolecular distance between the carbonyl moieties, is more prone to form a bidentate complex with a Li cation, which increased the contribution of the vehicle mechanism to Li ion diffusion even though similar AGGs and ionic clusters were also observed. The clear correlation between the unusual Li ion diffusion and the solvent-bridged, chain-like structure provides an important insight into the design principles for fast Li ion conducting liquid electrolytes that would enable Li ion transport decoupled from viscosity-controlled mass transfer processes. | |||||
書誌情報 |
Physical Chemistry Chemical Physics 巻 21, p. 5097-5105, 発行日 2019-03-07 |
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ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 14639076 | |||||
書誌レコードID | ||||||
収録物識別子タイプ | NCID | |||||
収録物識別子 | AA11301773 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | https://doi.org/10.1039/c9cp00425d | |||||
著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
出版者 | ||||||
出版者 | Royal Society of Chemistry |