WEKO3
アイテム
{"_buckets": {"deposit": "074bd250-0f82-489c-84db-544566a8750c"}, "_deposit": {"created_by": 3, "id": "9405", "owners": [3], "pid": {"revision_id": 0, "type": "depid", "value": "9405"}, "status": "published"}, "_oai": {"id": "oai:ynu.repo.nii.ac.jp:00009405", "sets": ["496"]}, "author_link": ["19251", "34826", "34833", "34830", "34834", "34832", "34828", "34831", "34827", "34829"], "item_2_biblio_info_8": {"attribute_name": "書誌情報", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "2018-11-29", "bibliographicIssueDateType": "Issued"}, "bibliographicIssueNumber": "47", "bibliographicPageEnd": "10745", "bibliographicPageStart": "10736", "bibliographicVolumeNumber": "122", "bibliographic_titles": [{"bibliographic_title": "Journal of Physical Chemistry B "}]}]}, "item_2_description_5": {"attribute_name": "抄録", "attribute_value_mlt": [{"subitem_description": "We demonstrate that Li+ hopping conduction, which cannot be explained by conventional models i.e. Onsager’s theory and Stokes’ law, emerges in highly concentrated liquid electrolytes composed of LiBF4 and sulfolane (SL). Self-diffusion coefficients of Li+ (DLi), BF4− (DBF4), and SL (DSL) were measured with pulsed field gradient NMR. In the concentrated electrolytes with molar ratios of SL/LiBF4 ≤ 3, the ratios DSL/DLi and DBF4/DLi become lower than 1, suggesting faster diffusion of Li+ than SL and BF4−, and thus the evolution of Li+ hopping conduction. X-ray crystallographic analysis of the LiBF4:SL (1:1) solvate revealed that the two oxygen atoms of the sulfone group are involved in bridging coordination of two different Li+ ions. In addition, the BF4− anion also participates in bridging coordination of Li+. Raman spectra of the highly concentrated LiBF4-SL solution suggested that Li+ ions are bridged by SL and BF4− even in the liquid state. Moreover, detailed investigation along with molecular dynamics simulations suggests that Li+ exchanges ligands (SL and BF4−) dynamically in the highly concentrated electrolytes, and Li+ hops from one coordination site to another. The spatial proximity of coordination sites, along with possible domain structure, is assumed to enable Li+ hopping conduction. Finally, we demonstrate that Li+ hopping suppresses concentration polarization in Li batteries, leading to increased limiting current density and improved rate capability compared to the conventional concentration electrolyte. Identification and rationalization of Li+ ion hopping in concentrated SL electrolytes is expected to trigger a new paradigm of understanding for such unconventional electrolyte systems. ", "subitem_description_type": "Abstract"}]}, "item_2_publisher_35": {"attribute_name": "出版者", "attribute_value_mlt": [{"subitem_publisher": "American Chemical Society"}]}, "item_2_relation_13": {"attribute_name": "DOI", "attribute_value_mlt": [{"subitem_relation_type": "isVersionOf", "subitem_relation_type_id": {"subitem_relation_type_id_text": "info:doi/10.1021/acs.jpcb.8b09439", "subitem_relation_type_select": "DOI"}}]}, "item_2_rights_14": {"attribute_name": "権利", "attribute_value_mlt": [{"subitem_rights": "© 2018 American Chemical Society"}]}, "item_2_source_id_9": {"attribute_name": "ISSN", "attribute_value_mlt": [{"subitem_source_identifier": "15206106", "subitem_source_identifier_type": "ISSN"}]}, "item_2_text_4": {"attribute_name": "著者所属", "attribute_value_mlt": [{"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST)"}, {"subitem_text_value": "Department of Materials Chemistry, Nagoya University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}, {"subitem_text_value": "Graduate School of Science and Technology, Niigata University"}, {"subitem_text_value": "Department of Chemistry and Biotechnology, Yokohama National University"}]}, "item_2_version_type_18": {"attribute_name": "著者版フラグ", "attribute_value_mlt": [{"subitem_version_resource": "http://purl.org/coar/version/c_ab4af688f83e57aa", "subitem_version_type": "AM"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "Dokko, Kaoru"}], "nameIdentifiers": [{"nameIdentifier": "34826", "nameIdentifierScheme": "WEKO"}, {"nameIdentifier": "70438117 ", "nameIdentifierScheme": "e-Rad", "nameIdentifierURI": "https://kaken.nii.ac.jp/ja/search/?qm=70438117 "}]}, {"creatorNames": [{"creatorName": "Watanabe, Daiki"}], "nameIdentifiers": [{"nameIdentifier": "34827", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Ugata, Yosuke"}], "nameIdentifiers": [{"nameIdentifier": "34828", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Thomas, Morgan L."}], "nameIdentifiers": [{"nameIdentifier": "34829", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Tsuzuki, Seiji"}], "nameIdentifiers": [{"nameIdentifier": "34830", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Shinoda, Wataru"}], "nameIdentifiers": [{"nameIdentifier": "34831", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Hashimoto, Kei"}], "nameIdentifiers": [{"nameIdentifier": "34832", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Ueno, Kazuhide"}], "nameIdentifiers": [{"nameIdentifier": "34833", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Umebayashi, Yasuhiro"}], "nameIdentifiers": [{"nameIdentifier": "34834", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Watanabe, Masayoshi"}], "nameIdentifiers": [{"nameIdentifier": "19251", "nameIdentifierScheme": "WEKO"}, {"nameIdentifier": "60158657", "nameIdentifierScheme": "e-Rad", "nameIdentifierURI": "https://kaken.nii.ac.jp/ja/search/?qm=60158657"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2019-11-30"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "acs.jpcb.pdf", "filesize": [{"value": "975.5 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 975500.0, "url": {"label": "acs.jpcb", "url": "https://ynu.repo.nii.ac.jp/record/9405/files/acs.jpcb.pdf"}, "version_id": "c6afe6a4-cd06-4e13-a7b3-0dd44c96e317"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "journal article", "resourceuri": "http://purl.org/coar/resource_type/c_6501"}]}, "item_title": "Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based Liquid Electrolytes", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based Liquid Electrolytes"}]}, "item_type_id": "2", "owner": "3", "path": ["496"], "permalink_uri": "http://hdl.handle.net/10131/00012075", "pubdate": {"attribute_name": "公開日", "attribute_value": "2018-11-14"}, "publish_date": "2018-11-14", "publish_status": "0", "recid": "9405", "relation": {}, "relation_version_is_last": true, "title": ["Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based Liquid Electrolytes"], "weko_shared_id": 3}
Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based Liquid Electrolytes
http://hdl.handle.net/10131/00012075
http://hdl.handle.net/10131/00012075ac6f9856-6844-4760-9e16-5e80079b1ec7
名前 / ファイル | ライセンス | アクション |
---|---|---|
acs.jpcb (975.5 kB)
|
|
Item type | 学術雑誌論文 / Journal Article(1) | |||||
---|---|---|---|---|---|---|
公開日 | 2018-11-14 | |||||
タイトル | ||||||
タイトル | Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based 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 |
Dokko, Kaoru
× Dokko, Kaoru× Watanabe, Daiki× Ugata, Yosuke× Thomas, Morgan L.× Tsuzuki, Seiji× Shinoda, Wataru× Hashimoto, Kei× Ueno, Kazuhide× Umebayashi, Yasuhiro× Watanabe, Masayoshi |
|||||
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 | ||||||
著者所属 | ||||||
Department of Chemistry and Biotechnology, Yokohama National University | ||||||
著者所属 | ||||||
Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST) | ||||||
著者所属 | ||||||
Department of Materials Chemistry, Nagoya 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 | ||||||
Graduate School of Science and Technology, Niigata 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 | We demonstrate that Li+ hopping conduction, which cannot be explained by conventional models i.e. Onsager’s theory and Stokes’ law, emerges in highly concentrated liquid electrolytes composed of LiBF4 and sulfolane (SL). Self-diffusion coefficients of Li+ (DLi), BF4− (DBF4), and SL (DSL) were measured with pulsed field gradient NMR. In the concentrated electrolytes with molar ratios of SL/LiBF4 ≤ 3, the ratios DSL/DLi and DBF4/DLi become lower than 1, suggesting faster diffusion of Li+ than SL and BF4−, and thus the evolution of Li+ hopping conduction. X-ray crystallographic analysis of the LiBF4:SL (1:1) solvate revealed that the two oxygen atoms of the sulfone group are involved in bridging coordination of two different Li+ ions. In addition, the BF4− anion also participates in bridging coordination of Li+. Raman spectra of the highly concentrated LiBF4-SL solution suggested that Li+ ions are bridged by SL and BF4− even in the liquid state. Moreover, detailed investigation along with molecular dynamics simulations suggests that Li+ exchanges ligands (SL and BF4−) dynamically in the highly concentrated electrolytes, and Li+ hops from one coordination site to another. The spatial proximity of coordination sites, along with possible domain structure, is assumed to enable Li+ hopping conduction. Finally, we demonstrate that Li+ hopping suppresses concentration polarization in Li batteries, leading to increased limiting current density and improved rate capability compared to the conventional concentration electrolyte. Identification and rationalization of Li+ ion hopping in concentrated SL electrolytes is expected to trigger a new paradigm of understanding for such unconventional electrolyte systems. | |||||
書誌情報 |
Journal of Physical Chemistry B 巻 122, 号 47, p. 10736-10745, 発行日 2018-11-29 |
|||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 15206106 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | info:doi/10.1021/acs.jpcb.8b09439 | |||||
権利 | ||||||
権利情報 | © 2018 American Chemical Society | |||||
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 | American Chemical Society |