Related Experiment Video
Updated: May 11, 2025

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering
Published on: April 17, 2018
Decoding the Competing Effects of Dynamic Solvation Structures on Nuclear Magnetic Resonance Chemical Shifts of
Qi You1, Yan Sun1,2, Feng Wang3
1State Key Laboratory of Physical Chemistry of Solid Surface, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Abstract:
Understanding the solvation structure of electrolytes is critical for optimizing the electrochemical performance of rechargeable batteries as it directly influences properties such as ionic conductivity, viscosity, and electrochemical stability. The highly complex structures and strong interactions in high-concentration electrolytes make accurate modeling and interpretation of their "structure-property" relationships even more challenging with spectroscopic methods. In this study, we present a machine learning-based approach to predict dynamic 7Li NMR chemical shifts in LiFSI/DME electrolyte solutions. Additionally, we provide a comprehensive structural analysis to interpret the observed chemical shift behavior in experiments, particularly the abrupt changes in 7Li chemical shifts at high concentrations. Using advanced modeling techniques, we quantitatively establish the relationship between the molecular structure and NMR spectrum, offering critical insights into solvation structure assignments. Our findings reveal the coexistence of two competing local solvation structures that shift in dominance as electrolyte concentration approaches the concentrated limit, leading to an anomalous reversal of 7Li NMR chemical shift in the experiment. This work provides a detailed molecular-level understanding of the intricate solvation structures probed by NMR spectroscopy, leading the way for an enhanced electrolyte design.
Related Concept Videos
Chemical Shift: Internal References and Solvent Effects
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
π Electron Effects on Chemical Shift: Overview
NMR Spectroscopy: Chemical Shift Overview
For instance, the proton...
Atomic Nuclei: Nuclear Relaxation Processes

