Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction?

Correction for ‘Comment on “Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction?” by M. Gouverneur, F. Schmidt and M. Schönhoff, Phys. Chem. Chem. Phys., 2018, 20, 7470’ by Kenneth R. Harris, Phys. Chem. Chem. Phys., 2018, 20, 30041–30045.

Download Full-text

Comment on “Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction?” by M. Gouverneur, F. Schmidt and M. Schönhoff,Phys. Chem. Chem. Phys., 2018,20, 7470

Physical Chemistry Chemical Physics ◽

10.1039/c8cp02595a ◽

2018 ◽

Vol 20 (47) ◽

pp. 30041-30045 ◽

Cited By ~ 6

Author(s):

Kenneth R. Harris

Keyword(s):

Ionic Liquid ◽

Liquid Mixtures ◽

Chem Phys ◽

Frame Of Reference ◽

Transference Numbers ◽

Transport Numbers ◽

Wrong Direction ◽

Phys Chem Chem Phys

Transport numbers from electrophoretic NMR must be converted to the correct frame of reference to be physically meaningful.

Download Full-text

Reply to the ‘Comment on “Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction?”’ by K. R. Harris,Phys. Chem. Chem. Phys., 2018,20, DOI: 10.1039/C8CP02595A

Physical Chemistry Chemical Physics ◽

10.1039/c8cp06075d ◽

2018 ◽

Vol 20 (47) ◽

pp. 30046-30052 ◽

Cited By ~ 3

Author(s):

Monika Schönhoff ◽

Cornelia Cramer ◽

Florian Schmidt

Keyword(s):

Ionic Liquid ◽

Reference Frame ◽

Liquid Mixtures ◽

Chem Phys ◽

Transference Numbers ◽

Negative Transference ◽

External Reference ◽

Wrong Direction ◽

Phys Chem Chem Phys

Irrespective of the choice of an internal or external reference frame, Li+cations may have negative transference numbers.

Download Full-text

General Trend of Negative Transference Number in Li Salt/Ionic Liquid Mixtures

10.26434/chemrxiv.7728545 ◽

2019 ◽

Cited By ~ 1

Author(s):

Nicola Molinari ◽

Jonathan P. Mailoa ◽

Boris Kozinsky

Keyword(s):

Ionic Liquid ◽

Transference Number ◽

Liquid Mixtures ◽

Single Linkage ◽

Self Diffusion ◽

Wide Range ◽

Single Linkage Cluster ◽

Concentrated Solution ◽

The One ◽

Dynamics Simulations

We show that strong cation-anion interactions in a wide range of lithium-salt/ionic liquid mixtures result in a negative lithium transference number, using molecular dynamics simulations and rigorous concentrated solution theory. This behavior fundamentally deviates from the one obtained using self-diffusion coefficient analysis and agrees well with experimental electrophoretic NMR measurements, which accounts for ion correlations. We extend these findings to several ionic liquid compositions. We investigate the degree of spatial ionic coordination employing single-linkage cluster analysis, unveiling asymmetrical anion-cation clusters. Additionally, we formulate a way to compute the effective lithium charge that corresponds to and agrees well with electrophoretic measurements and show that lithium effectively carries a negative charge in a remarkably wide range of chemistries and concentrations. The generality of our observation has significant implications for the energy storage community, emphasizing the need to reconsider the potential of these systems as next generation battery electrolytes.<br>

Download Full-text

Rapid relaxation NMR measurements to predict rate coefficients in ionic liquid mixtures. An examination of reaction outcome changes in a homologous series of ionic liquids

Physical Chemistry Chemical Physics ◽

10.1039/d0cp06066f ◽

2021 ◽

Author(s):

Daniel C Morris ◽

Stuart W Prescott ◽

Jason B Harper

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Homologous Series ◽

Rate Coefficient ◽

Liquid Mixtures ◽

Solvent Mixture ◽

Rate Coefficients ◽

Substitution Process

A series of ionic liquids based on the 1-alkyl-3-methylimidazolium cations were examined as components of the solvent mixture for a bimolecular substitution process. The effects on both the rate coefficient...

Download Full-text