Ion speciation of lithium hexafluorophosphate in dimethyl carbonate solutions: an infrared spectroscopy study
Literature Information
Kristen D. Fulfer, Daniel G. Kuroda
Solutions of lithium hexafluorophosphate (LiPF6) in linear organic carbonates play a significant role in the portable energy storage industry. However, many questions remain about the solution structure at the molecular-level. An atomic characterization of these solutions is important for determining their structure–property relations, which will allow for the rational design of new and improved lithium ion based energy storage technologies. In this study, a combination of infrared spectroscopies and density functional theory calculations was used to investigate the speciation of the lithium ion (free ion, solvent separated ion pair, contact ion pairs, and aggregates) in dimethyl carbonate solutions having concentrations ranging from 1 M to 3 M. The experimental data shows that at typical battery electrolyte concentrations the lithium ion exists predominantly as free ions and solvent separated ion pairs, but charged contact ion pairs are also present in small concentrations. In contrast, at high concentrations the lithium ion is present in aggregates, but a noticeable fraction remains present as free ions.
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Physical Chemistry Chemical Physics

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.

![[(1S,2S,3R,4S,7R,9S,10S,12R,15S)-4,12-Diacetyloxy-15-[(2R,3S)-3-benzamido-3-phenyl-2-(2,2,2-trichloroethoxycarbonyloxy)propanoyl]oxy-1,9-dihydroxy-10,14,17,17-tetramethyl-11-oxo-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-2-yl] benzoate structure [(1S,2S,3R,4S,7R,9S,10S,12R,15S)-4,12-Diacetyloxy-15-[(2R,3S)-3-benzamido-3-phenyl-2-(2,2,2-trichloroethoxycarbonyloxy)propanoyl]oxy-1,9-dihydroxy-10,14,17,17-tetramethyl-11-oxo-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-2-yl] benzoate structure](https://static.chemtradehub.com/structs/100/100431-55-8-7104.webp)


