Quantification of cation–cation, anion–anion and cation–anion correlations in Li salt/glyme mixtures by combining very-low-frequency impedance spectroscopy with diffusion and electrophoretic NMR
Literature Information
Sandra Pfeifer, Florian Ackermann, Fabian Sälzer, Monika Schönhoff, Bernhard Roling
Directional correlations between the movements of cations and anions exert a strong influence on the charge and mass transport properties of concentrated battery electrolytes. Here, we combine, for the first time, very-low-frequency impedance spectroscopy on symmetrical Li|electrolyte|Li cells with diffusion and electrophoretic NMR in order to quantify cation–cation, anion–anion and cation–anion correlations in Li salt/tetraglyme (G4) mixtures with Li salt to G4 ratios between 1 : 1 and 1 : 2. We find that all correlations are negative, with like-ion anticorrelations (cation–cation and anion–anion) being generally stronger than cation–anion anticorrelations. In addition, we observe that like-ion anticorrelations are stronger for the heavier type of ion and that all anticorrelations become weaker with decreasing Li salt to G4 ratio. These findings are in contrast to theories considering exclusively anion–cation correlations in form of ion pairs, as the latter imply positive cation–anion correlations. We analyze in detail the influence of anticorrelations on Li+ transference numbers and on the Haven ratio. In order to rationalize our results, we derive linear response theory expressions for all ion correlations. These expressions show that the Li+ ion transport under anion-blocking conditions in a battery is governed by equilibrium center-of-mass fluctuations in the electrolytes. This suggests that in future electrolyte theories and computer simulations, more attention should be paid to equilibrium center-of-mass fluctuations.
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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.














