Direct determination of ionic transference numbers in ionic liquids by electrophoretic NMR

Literature Information

Publication Date 2015-10-27
DOI 10.1039/C5CP05753A
Impact Factor 3.676
Authors

Martin Gouverneur, Jakob Kopp, Leo van Wüllen, Monika Schönhoff


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Abstract

Charge transport in ionic liquids is a phenomenon of utmost interest for electrochemical (e.g. battery) applications, but also of high complexity, involving transport of ion pairs, charged clusters and single ions. Molecular understanding is limited due to unknown contributions of cations, anions and clusters to the conductivity. Here, we perform electrophoretic NMR to determine electrophoretic mobilities of cations and anions in seven different ionic liquids. For the first time, mobilities in the range down to 10−10 m2 V−1 s−1 are determined. The ionic transference number, i.e. the fractional contribution of an ionic species to overall conductivity, strongly depends on cation and anion structure and its values show that structurally very similar ionic liquids can have cation- or anion-dominated conductivity. Transference numbers of cations, for example, vary from 40% to 58%. The results further prove the relevance of asymmetric clusters like [CationXAnionY]X−Y, X ≠ Y, for charge transport in ionic liquids.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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