Solvate Ionic Liquids at Electrified Interfaces

Yu, Zhou; Fang, Chao; Huang, Jingsong; Sumpter, Bobby G.; Qiao, Rui

doi:10.1021/acsami.8b10387

Solvate Ionic Liquids at Electrified Interfaces

Journal Article · Wed Aug 29 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b10387· OSTI ID:1474513

Yu, Zhou ^[1]; Fang, Chao ^[1]; ^[2]; ^[2]; ^[1]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Solvate ionic liquids (SILs) are a promising electrolyte for Li-ion batteries; thus, their behavior at electrified interfaces is crucial for the operation of these batteries. We report molecular dynamics simulation results for a prototypical SIL of lithium triglyme bis(trifluoro-methanesulfonyl)imide ([Li(G3)][TFSI]) sandwiched between electrified surfaces. At negatively charged as well as neutral electrodes, the electrolyte largely maintains the characteristics of SILs, e.g., a majority of the interfacial Li⁺ ions remains coordinated by the similar number of oxygen atoms on G3 ligands as the bulk Li⁺ ions. The persistence of the complex ions is attributed to the 1:1 Li-G3 ratio in bulk SILs and the fact that G3 molecules readily adapt to the interfacial environment, e.g., by aligning themselves with the surface to ensure good solvation of the interfacial Li⁺ ions. Nevertheless, the interfacial Li⁺ ions also display changes of solvation from that in bulk SIL by deviating from the molecular plane formed by the oxygen atoms on G3 ligands as electrodes become more negatively charged. Using density functional theory along with natural bond orbital calculations, we examine the effects of such structural distortion on the properties of the complex cation. Both the frontier orbital energies of the complex cation and the donor-acceptor interactions between Li⁺ ions and G3 ligands are found to be dependent on the deviation of Li⁺ ions from the molecular plane of the G3 ligands, which suggest that the reduction of Li⁺ ions should be facilitated by the structural distortion. These results bear important implications for the nanostructures and properties of SILs near electrified interfaces during actual operations of Li-ion batteries and serve to provide guidance toward the rational design of new SILs electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1474513

Alternate ID(s):: OSTI ID: 1482436

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 38 Vol. 10; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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