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Systematic Investigation of Classical Molecular Dynamics Models for Ionic Liquid-Based Electrolytes at Electrode
Sreehari Batni Ravindranath1, Jhonatan Soto Puelles1, Agilio Padua2
1Institute for Frontier Materials, Deakin University, Burwood, Australia.
Summary
Molecular dynamics (MD) simulations of ionic liquid (IL) electrolytes reveal that electrode modeling choices significantly impact results. Careful selection of constant charge (CCM) or constant potential (CPM) models and force fields is crucial for accurate battery interface predictions.
Area of Science:
- Computational chemistry
- Electrolyte science
- Materials science
Background:
- Molecular dynamics (MD) simulations are vital for studying ionic liquid (IL) electrolytes at electrified electrode interfaces.
- Methodological choices in MD simulations, particularly electrode models and force fields, significantly influence predicted interfacial nanostructure and chemistry.
- Understanding the impact of these choices is crucial for accurate battery performance predictions.
Purpose of the Study:
- To systematically evaluate the constant charge model (CCM) and constant potential model (CPM) for electrode modeling in IL electrolytes.
- To assess the role of force field polarisability in capturing potential-dependent interfacial structure and chemistry.
- To provide guidance on methodological choices for modeling IL-electrode interfaces relevant to battery applications.
Main Methods:
- Systematic evaluation of CCM and CPM electrode modeling approaches.
- Inclusion of non-polarisable force fields (NPFF) and polarisable force fields (PFF).
- Simulation of neat ILs, salt-containing ILs, and hybrid systems with cosolvents or mixed cations.
Main Results:
- CCM and CPM with NPFF showed consistent results for ion layering and composition in neat and salt-containing ILs, with minor differences in ion orientation.
- Notable discrepancies in solvent behavior were observed for hybrid ILs with cosolvents.
- Distinct interfacial responses between NPFF and PFF were identified for mixed-cation ILs, necessitating caution.
Conclusions:
- Methodological choices in MD simulations significantly affect the predicted interfacial properties of IL electrolytes.
- CCM and CPM can yield consistent results for simpler IL systems with NPFF.
- Hybrid ILs and mixed-cation ILs require careful consideration of force field polarisability and model selection for accurate simulation outcomes.
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