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Updated: May 9, 2026
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How solvent activity and solute solvation control electrode potentials: quantitative insights from Li+ insertion into
Ludivine K/Bidi1, Tom Rocca1, Lucie Chen1
1Université Paris Cité, CNRS, ITODYS Paris F-75013 France limoges@u-paris.fr.
Chemical Science
|May 8, 2026
Summary
Adjusting electrolyte salt concentration improves battery performance by reducing side reactions. A new thermodynamic framework predicts electrode potential shifts based on salt and solvent activity and hydration numbers.
Area of Science:
- Electrochemistry
- Materials Science
- Battery Technology
Background:
- Electrolyte salt concentration is a key factor influencing rechargeable battery performance.
- Parasitic side reactions in batteries are often linked to electrolyte composition.
- Predicting electrode potential variations with electrolyte concentration is crucial for battery design.
Purpose of the Study:
- To introduce and validate a thermodynamic framework for predicting electrode potential changes with electrolyte concentration.
- To incorporate electrolyte-specific parameters like salt and solvent activities and hydration numbers into a modified Nernst equation.
- To establish a generalizable method for understanding electrolyte concentration effects in electrochemical systems.
Main Methods:
- Developed a modified Nernst equation incorporating salt activity, solvent activity, and salt hydration number.
- Applied the framework to reversible lithium-ion insertion into anatase titanium dioxide (TiO2) using aqueous lithium chloride (LiCl) electrolytes.
- Combined experimental and theoretical data for water and LiCl activities and concentration-dependent hydration numbers.
Main Results:
- Achieved quantitative agreement between predicted and experimentally measured electrode potential shifts.
- Demonstrated the framework's ability to rationalize and predict potential variations across different electrolyte concentrations.
- Validated the thermodynamic approach for aqueous LiCl electrolytes and Li+ insertion into TiO2.
Conclusions:
- The validated thermodynamic framework provides a reliable method for controlling electrolyte concentration effects in batteries.
- This approach is broadly applicable to various electrochemical systems utilizing concentrated electrolytes.
- Understanding and tuning electrolyte concentration is essential for enhancing battery performance and mitigating side reactions.
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