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The effect of lithium salt doping on the nanostructure of ionic liquids

Author

  • Luis Aguilera
  • Johannes Volkner
  • Ana Labrador
  • Aleksandar Matic

Summary, in English

In this work we report on the evolution of the structure of two model ionic liquid families, N-alkyl-N-methylpyrrolidinium (Pyr(1n)-TFSI) and 1-alkyl-3-methylimidazolium (C(n)MIm-TFSI) (n = 3, 4, 6 and 8) both containing the bis(trifluoromethanesulfonyl)imide (TFSI) anion, upon the addition of LiTFSI using small angle X-ray scattering (SAXS). The introduction of a lithium salt (Li-salt) tunes the interactions through the substitution of the large cation in the ionic liquid with the small and charge localized lithium ion, thus increasing the coulombic contribution from ion-ion interactions. We find that the introduction of lithium ions results in a restructuring of the polar groups in the ionic liquids. These changes are manifested as an increase in the correlation lengths related to charge alternation of the ions and a more disordered structure. This restructuring is interpreted as a reconfiguration of the anions as they coordinate to the small and ionic lithium. In contrast, the length scale of the mesoscopic heterogeneities related to the clustering of alkyl chains is virtually unchanged with lithium doping. Moreover, the correlation corresponding to alkyl chain domains becomes more well defined with increasing salt concentration, suggesting that Li-salt doping, i.e. an increased columbic interaction in the system, promotes clustering of the alkyl tails.

Department/s

Publishing year

2015

Language

English

Pages

27082-27087

Publication/Series

Physical Chemistry Chemical Physics

Volume

17

Issue

40

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Physical Chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9084