Li + Solvation and Ionic Transport in Lithium Solvate Ionic Liquids Diluted by Molecular Solvents
Abstract
An equimolar mixture of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and either triglyme (G3) or tetraglyme (G4) yielded stable molten complexes: [Li(G3)][TFSA] and [Li(G4)][TFSA]. These are known as solvate ionic liquids (SILs). Glyme-based SILs have thermal and electrochemical properties favorable for use as lithium-conducting electrolytes in lithium batteries. However, their intrinsically high viscosities and low ionic conductivities prevent practical application. Therefore, we diluted SILs with molecular solvents in order to enhance their ionic conductivities. To determine the stabilities of the complex cations in diluted SILs, their conductivity and viscosity, the self-diffusion coefficients, and Raman spectra were measured. [Li(G3)] + and [Li(G4)] + were stable in nonpolar solvents, that is, toluene, diethyl carbonate, and a hydrofluoroether (HFE); however, ligand exchange took place between glyme and solvent when polar solvents, that is, water and propylene carbonate, were used. In acetonitrile (AN) mixed solvent complex cations [Li(G3)(AN)] + and [Li(G4)(AN)] + were formed. [Li(G4)][TFSA] was more conductive than [Li(G3)][TFSA] when diluted with nonpolar solvents due to the greater ionic dissociativity in [Li(G4)][TFSA] mixtures. In view of the stability of the Li–glyme complex cations, the enhanced ionic conductivities, and the intrinsic electrochemical stabilities of the diluting solvents, [Li(G4)][TFSA] diluted by toluene or HFE, can be a candidate for an…
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The disadvantage of a tightly bound ether solvation cage could be partially overcome by increasing salt concentration, where Li+ approaches a solvated electrolyte state and desolvation energy becomes minimized by close solvation cages or contact-ion pairs.
“However, the disadvantage of a tightly bound ether solvation cage could be partially overcome by increasing the salt concentration, in which the Li + approaches a solvated electrolyte state, as suggested by Watanabe et al. [55], and the desolvation energy becomes minimized by the closely solvation cages or contact-ionpairs (CIPs).”
From Review on Low-Temperature Electrolytes for Lithium-Ion and Lithium Metal Batteries (2023) · cites this paper as [55]
Cites
Electrolytes and Interphases in Li-Ion Batteries and Beyond
Xu, K. (2014) · Chemical Reviews · doi:10.1021/cr500003w · Cited by 5,566 · see citing works
High rate and stable cycling of lithium metal anode
Qian, J., Henderson, W. A., Xu, W., Bhattacharya, P., Engelhard, M., Borodin, O., & Zhang, J.-G. (2015) · Nature Communications · doi:10.1038/ncomms7362 · Cited by 2,561 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
High-Efficiency Lithium Metal Batteries with Fire-Retardant Electrolytes
Chen, S., Zheng, J., Yu, L., Ren, X., Engelhard, M. H., Niu, C., Lee, H., Xu, W., Xiao, J., Liu, J., et al. (2018) · Joule · doi:10.1016/j.joule.2018.05.002 · Cited by 654 · see citing works
Review on Low-Temperature Electrolytes for Lithium-Ion and Lithium Metal Batteries
Tan, S., Shadike, Z., Cai, X., Lin, R., Kludze, A., Borodin, O., Lucht, B. L., Wang, C., Hu, E., Xu, K., et al. (2023) · Electrochemical Energy Reviews · doi:10.1007/s41918-023-00199-1 · Cited by 118 · see citing works
“…bound ether solvation cage could be partially overcome by increasing the salt concentration, in which the Li + approaches a solvated electrolyte state, as suggested by Watanabe et al. [55], and the desolvation energy becomes minimized by the closely solvation cages or contact-ion-pairs (CIPs).”
- Authors
- Ueno, K., Murai, J., Ikeda, K., Tsuzuki, S., Tsuchiya, M., Tatara, R., Mandai, T., Umebayashi, Y., Dokko, K., & Watanabe, M.
- Affiliations
- Yamaguchi University (JP)
- Yokohama National University (JP)
- National Institute of Advanced Industrial Science and Technology (JP)
- Niigata University (JP)
- Corresponding author
- Watanabe, Masayoshi
- ORCID
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-12-29
- Volume
- 120
- Issue
- 29
- Pages
- 15792-15802
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- OpenAlex
- W2214748933
- Cited by
- 149
- References
- 2
- Citations by year
- 2026: 9 · 2025: 13 · 2024: 13 · 2023: 12 · 2022: 18 · 2021: 13 · 2020: 13 · 2019: 16 · 2018: 19 · 2017: 12 · 2016: 11
- FWCI
- 6.75
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry C (publishedVersion)
- Funders
- ALCA-SPRING, Japan Science and Technology Agency (JST)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Advanced Battery Materials and Technologies
- Physical Sciences › Chemical Engineering › Catalysis › Ionic liquids properties and applications
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Advancements in Battery Materials
- Keywords
- solvate ionic liquids, ionic conductivity, viscosity, self-diffusion coefficient, ligand exchange, hydrofluoroethers, toluene, acetonitrile, lithium battery electrolytes, electrochemical stability, Raman spectra
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
