NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism
The dynamics in mixtures of ionic liquid and monoatomic cations has been studied at different time scales ranging from the nanosecond up to the second. The mixtures were composed of cholinium bis(trifluoromethanesulfonyl)imide ([Chol][TFSI]) and LiTFSI, with LiTFSI mole fraction, Image 1, spanning f...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2024-06-01
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| Series: | Journal of Ionic Liquids |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2772422024000107 |
| _version_ | 1827221575753007104 |
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| author | Ousmane Karé Antonio De Souza Braga Neto Baptiste Rigaud Quentin Berrod Sandrine Lyonnard Clément Cousin Juliette Sirieix-Plénet Anne-Laure Rollet Guillaume Mériguet |
| author_facet | Ousmane Karé Antonio De Souza Braga Neto Baptiste Rigaud Quentin Berrod Sandrine Lyonnard Clément Cousin Juliette Sirieix-Plénet Anne-Laure Rollet Guillaume Mériguet |
| author_sort | Ousmane Karé |
| collection | DOAJ |
| description | The dynamics in mixtures of ionic liquid and monoatomic cations has been studied at different time scales ranging from the nanosecond up to the second. The mixtures were composed of cholinium bis(trifluoromethanesulfonyl)imide ([Chol][TFSI]) and LiTFSI, with LiTFSI mole fraction, Image 1, spanning from 0 to 0.5 (saturated solution), and [Chol][TFSI] and Image 2 from 0 to 0.12. The translational self-diffusion coefficients of Image 3, Image 4 and Image 5 have been measured, along with NMR their relaxation times at various magnetic fields, in order to decipher the intertwined dynamics between the ions, and to reveal how the local dynamics impact the long range translational diffusion. When the concentrations of lithium and lanthanum are increased in the liquid, the long range dynamics of all the ions drop. In the case of LiTFSI, the self-diffusion coefficient of lithium becomes higher than the one of TFSI at high concentration, revealing a change in lithium transport mechanisms. The NMR relaxation data confirm this change, showing a clearer transition at Image 6. It is interpreted as a change from a vehicular transport mechanism of the lithium below Image 6 to a hopping mechanism above. A similar crossover seems to occur in the lanthanum solutions. This phenomenon seems correlated to the departure of the hydroxyl group of the organic cation from the lithium solvation shell. |
| first_indexed | 2024-04-24T17:26:48Z |
| format | Article |
| id | doaj.art-42980fe7eb0e464db8905753f6a79205 |
| institution | Directory Open Access Journal |
| issn | 2772-4220 |
| language | English |
| last_indexed | 2025-03-21T16:24:47Z |
| publishDate | 2024-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Journal of Ionic Liquids |
| spelling | doaj.art-42980fe7eb0e464db8905753f6a792052024-06-17T06:00:39ZengElsevierJournal of Ionic Liquids2772-42202024-06-0141100087NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanismOusmane Karé0Antonio De Souza Braga Neto1Baptiste Rigaud2Quentin Berrod3Sandrine Lyonnard4Clément Cousin5Juliette Sirieix-Plénet6Anne-Laure Rollet7Guillaume Mériguet8Sorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, FranceSorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, FranceSorbonne Université, Fédération de Chimie et Matériaux de Paris Centre (FCMAT), 4 Place Jussieu, Paris, FranceUniversité Grenoble Alpes, CNRS, CEA, IRIG-SyMMES, 17 avenue des Martyrs, Grenoble, FranceUniversité Grenoble Alpes, CNRS, CEA, IRIG-SyMMES, 17 avenue des Martyrs, Grenoble, FranceSorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, FranceSorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, FranceSorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, France; Corresponding author.Sorbonne Université/CNRS, Laboratoire Physico-Chimie des Électrolytes et Nano-Systèmes Interfaciaux (PHENIX), 4 place Jussieu, Paris, France; Corresponding author.The dynamics in mixtures of ionic liquid and monoatomic cations has been studied at different time scales ranging from the nanosecond up to the second. The mixtures were composed of cholinium bis(trifluoromethanesulfonyl)imide ([Chol][TFSI]) and LiTFSI, with LiTFSI mole fraction, Image 1, spanning from 0 to 0.5 (saturated solution), and [Chol][TFSI] and Image 2 from 0 to 0.12. The translational self-diffusion coefficients of Image 3, Image 4 and Image 5 have been measured, along with NMR their relaxation times at various magnetic fields, in order to decipher the intertwined dynamics between the ions, and to reveal how the local dynamics impact the long range translational diffusion. When the concentrations of lithium and lanthanum are increased in the liquid, the long range dynamics of all the ions drop. In the case of LiTFSI, the self-diffusion coefficient of lithium becomes higher than the one of TFSI at high concentration, revealing a change in lithium transport mechanisms. The NMR relaxation data confirm this change, showing a clearer transition at Image 6. It is interpreted as a change from a vehicular transport mechanism of the lithium below Image 6 to a hopping mechanism above. A similar crossover seems to occur in the lanthanum solutions. This phenomenon seems correlated to the departure of the hydroxyl group of the organic cation from the lithium solvation shell.http://www.sciencedirect.com/science/article/pii/S2772422024000107Ionic liquidElectrolyteDiffusionNMR relaxationFast field cycling relaxometrySolvation |
| spellingShingle | Ousmane Karé Antonio De Souza Braga Neto Baptiste Rigaud Quentin Berrod Sandrine Lyonnard Clément Cousin Juliette Sirieix-Plénet Anne-Laure Rollet Guillaume Mériguet NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism Journal of Ionic Liquids Ionic liquid Electrolyte Diffusion NMR relaxation Fast field cycling relaxometry Solvation |
| title | NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism |
| title_full | NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism |
| title_fullStr | NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism |
| title_full_unstemmed | NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism |
| title_short | NMR investigation of multi-scale dynamics in ionic liquids containing Li+ and La3+: From vehicular to hopping transport mechanism |
| title_sort | nmr investigation of multi scale dynamics in ionic liquids containing li and la3 from vehicular to hopping transport mechanism |
| topic | Ionic liquid Electrolyte Diffusion NMR relaxation Fast field cycling relaxometry Solvation |
| url | http://www.sciencedirect.com/science/article/pii/S2772422024000107 |
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