Various electrical double layer (EDL) models have been proposed but mainly for homogenous solutions. Recently, the so-called Localized high-concentration electrolytes (LHCE) have shown many benefits to high-capacity electrodes. Recently, we have proposed micelle-like structures to enable a complete understanding of microstructures in LHCE, which contains a salt, solvent, and non-ion-solvating diluent, analogical to the roles of oil, surfactant, and water as in micelles. [1] As the solid electrolyte interphase (SEI) formation is sensitive to the EDL structure, [2] it is critical to understand the EDL structures for LHCE with heterogeneous structures.Molecular dynamics simulations were performed in several electrolytes with heterogeneous structures on negatively charged surfaces. It was found the Stern model with an absorbed cation layer adsorption layer and a more diffused layer with cation, anion, solvent, and diluents, should be used to describe the EDL of this type of electrolyte.For the system consisting of LiFSI salt, DME solvent, and TFEO diluent at a concentration of LiFSI-1.2DME-2TFEO, the heterogeneous micelle-like structures in LHCE are maintained in the EDL, with the Li+-rich salt-solvent clusters and the Li+-poor diluent regions. The diluent region contains Li+ near the negatively charged surface but does not have any ions in the bulk of LHCE. This is because TFEO cannot form a complete solvation shell in the bulk electrolyte due to the steric effect, however, only a partial solvation shell is needed in the Stern layer in the EDL. The appearance of Li+ in the diluent is also necessary for the EDL, as TFEO alone cannot screen the charge.The chemical and concentration design space for the three components is very large. To obtain a more general picture, we also explored different salt-solvent ratios and different diluent-salt interactions. As the salt solvent ratio increases from low (LCE), to medium (MCE) to high concentration electrolytes (HCE), where all solvents are coordinated with ions, the salt-solvent structures evolve from fully solvated ions or ion pairs in LCE, 3D branched networks in MCE, to fully connected salt aggregates in HCE. The salt-diluent interactions and diluent concentration further modify the micelle-like structures. The EDL for both LHCE and LMCE are heterogenous. [1] Nature Materials 22, 1531–1539 (2023)[2] J. Am. Chem. Soc. 145, 4, 2473–2484 (2023)
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