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Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries

Solvate ionic liquids (SILs), comprising long-lived, Li solvate cations and counter anions, serve as highly Li-ion-conductive and non-flammable electrolytes for use in lithium secondary batteries. In this work, we synthesized a series of novel redox-active glyme(oligoether)–Li salt-based SILs, consi...

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Autores principales: Kemmizaki, Yuta, Katayama, Yu, Tsutsumi, Hiromori, Ueno, Kazuhide
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9048989/
https://www.ncbi.nlm.nih.gov/pubmed/35492641
http://dx.doi.org/10.1039/c9ra10149g
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author Kemmizaki, Yuta
Katayama, Yu
Tsutsumi, Hiromori
Ueno, Kazuhide
author_facet Kemmizaki, Yuta
Katayama, Yu
Tsutsumi, Hiromori
Ueno, Kazuhide
author_sort Kemmizaki, Yuta
collection PubMed
description Solvate ionic liquids (SILs), comprising long-lived, Li solvate cations and counter anions, serve as highly Li-ion-conductive and non-flammable electrolytes for use in lithium secondary batteries. In this work, we synthesized a series of novel redox-active glyme(oligoether)–Li salt-based SILs, consisting of a symmetric ([Li(G3)](+)) or asymmetric ([Li(G3Bu)](+)) triglyme–Li salt complex and redox-active tetrahalogenoferrate ([FeX](−) (X = Br(4), Cl(3)Br, Cl(4))), for use as the catholyte in semi-liquid lithium secondary batteries. The successful formation of stable molten complexes of [Li(G3/G3Bu)][FeX] was confirmed by Raman spectroscopy and thermogravimetry. The melting point (T(m)) depended on both the molecular weights of the complex anions and the structures of the complex cations. [Li(G3)][FeCl(4)] comprised complex cations with a symmetric structure, and the smallest complex anions showed the lowest T(m) of 28.2 °C. The redox properties of the [FeX](−)/[FeX](2−) couple strongly suggested the suitability of [Li(G3/G3Bu)][FeX] as a catholyte. The discharge capacities of semi-liquid lithium secondary batteries utilizing the [Li(G3/G3Bu)][FeX] catholyte depended on the structure of the SILs, and the cell with [Li(G3)][FeCl(4)] showed the highest capacity with relatively good capacity retention. This study confirmed the feasibility of the glyme-based redox-active SILs as catholytes for scalable redox-flow type batteries.
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spelling pubmed-90489892022-04-28 Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries Kemmizaki, Yuta Katayama, Yu Tsutsumi, Hiromori Ueno, Kazuhide RSC Adv Chemistry Solvate ionic liquids (SILs), comprising long-lived, Li solvate cations and counter anions, serve as highly Li-ion-conductive and non-flammable electrolytes for use in lithium secondary batteries. In this work, we synthesized a series of novel redox-active glyme(oligoether)–Li salt-based SILs, consisting of a symmetric ([Li(G3)](+)) or asymmetric ([Li(G3Bu)](+)) triglyme–Li salt complex and redox-active tetrahalogenoferrate ([FeX](−) (X = Br(4), Cl(3)Br, Cl(4))), for use as the catholyte in semi-liquid lithium secondary batteries. The successful formation of stable molten complexes of [Li(G3/G3Bu)][FeX] was confirmed by Raman spectroscopy and thermogravimetry. The melting point (T(m)) depended on both the molecular weights of the complex anions and the structures of the complex cations. [Li(G3)][FeCl(4)] comprised complex cations with a symmetric structure, and the smallest complex anions showed the lowest T(m) of 28.2 °C. The redox properties of the [FeX](−)/[FeX](2−) couple strongly suggested the suitability of [Li(G3/G3Bu)][FeX] as a catholyte. The discharge capacities of semi-liquid lithium secondary batteries utilizing the [Li(G3/G3Bu)][FeX] catholyte depended on the structure of the SILs, and the cell with [Li(G3)][FeCl(4)] showed the highest capacity with relatively good capacity retention. This study confirmed the feasibility of the glyme-based redox-active SILs as catholytes for scalable redox-flow type batteries. The Royal Society of Chemistry 2020-01-24 /pmc/articles/PMC9048989/ /pubmed/35492641 http://dx.doi.org/10.1039/c9ra10149g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Kemmizaki, Yuta
Katayama, Yu
Tsutsumi, Hiromori
Ueno, Kazuhide
Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title_full Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title_fullStr Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title_full_unstemmed Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title_short Redox-active glyme–Li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
title_sort redox-active glyme–li tetrahalogenoferrate(iii) solvate ionic liquids for semi-liquid lithium secondary batteries
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9048989/
https://www.ncbi.nlm.nih.gov/pubmed/35492641
http://dx.doi.org/10.1039/c9ra10149g
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AT tsutsumihiromori redoxactiveglymelitetrahalogenoferrateiiisolvateionicliquidsforsemiliquidlithiumsecondarybatteries
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