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Mesoscopic Inhomogeneities in Concentrated Electrolytes.

ABSTRACT: A mesoscopic theory for water-in-salt electrolytes combining density functional and field-theoretic methods is developed in order to explain the unexpectedly large period of the oscillatory decay of the disjoining pressure observed in recent experiments for the lithium bis(trifluoromethylsulfonyl)-imide (LiTFSI) salt [T. S. Groves et al., J. Phys. Chem. Lett. 2021, 12, 1702]. We assumed spherical ions with different diameters and implicit solvent, inducing strong, short-range attraction between ions of the same sign. For this highly simplified model, we calculated correlation functions. Our results indicate that mesoscopic inhomogeneities can occur when the sum of the Coulomb and the water-mediated interactions between like ions is attractive at short and repulsive at large distances. We adjusted the attractive part of the potential to the water-in-LiTFSI electrolyte and obtained both the period and the decay rate of the correlations, in semiquantitative agreement with the experiment. In particular, the decay length of the correlations increases nearly linearly with the volume fraction of ions.

SUBMITTER: Patsahan O

PROVIDER: S-EPMC8892908 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Mesoscopic Inhomogeneities in Concentrated Electrolytes.

Patsahan Oksana O Ciach Alina A

ACS omega 20220216 8

A mesoscopic theory for water-in-salt electrolytes combining density functional and field-theoretic methods is developed in order to explain the unexpectedly large period of the oscillatory decay of the disjoining pressure observed in recent experiments for the lithium bis(trifluoromethylsulfonyl)-imide (LiTFSI) salt [T. S. Groves et al., J. Phys. Chem. Lett. 2021, 12, 1702]. We assumed spherical ions with different diameters and implicit solvent, inducing strong, short-rang ...[more]

PMID: 35252660

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Project description:Dual-ion batteries (DIBs) generally operate beyond 4.7 V vs Li+/Li0 and rely on the intercalation of both cations and anions in graphite electrodes. Major challenges facing the development of DIBs are linked to electrolyte decomposition at the cathode-electrolyte interface (CEI), graphite exfoliation, and corrosion of Al current collectors. In this work, X-ray photoelectron spectroscopy (XPS) is employed to gain a broad understanding of the nature and dynamics of the CEI built on anion-intercalated graphite cycled both in highly concentrated electrolytes (HCEs) of common lithium salts (LiPF6, LiFSI, and LiTFSI) in carbonate solvents and in a typical ionic liquid. Though Al metal current collectors were adequately stable in all HCEs, the Coulombic efficiency was substantially higher for HCEs based on LiFSI and LiTFSI salts. Specific capacities ranging from 80 to 100 mAh g-1 were achieved with a Coulombic efficiency above 90% over extended cycling, but cells with LiPF6-based electrolytes were characterized by <70% Coulombic efficiency and specific capacities of merely ca. 60 mAh g-1. The poor performance in LiPF6-containing electrolytes is indicative of the continual buildup of decomposition products at the interface due to oxidation, forming a thick interfacial layer rich in LixPFy, POxFy, LixPOyFz, and organic carbonates as evidenced by XPS. In contrast, insights from XPS analyses suggested that anion intercalation and deintercalation processes in the range from 3 to 5.1 V give rise to scant or extremely thin surface layers on graphite electrodes cycled in LiFSI- and LiTFSI-containing HCEs, even allowing for probing anions intercalated in the near-surface bulk. In addition, ex situ Raman, SEM and TEM characterizations revealed the presence of a thick coating on graphite particles cycled in LiPF6-based electrolytes regardless of salt concentration, while hardly any surface film was observed in the case of concentrated LiFSI and LiTFSI electrolytes.

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Mesoscopic Inhomogeneities in Concentrated Electrolytes.

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Mesoscopic Inhomogeneities in Concentrated Electrolytes.

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