Nano-Plasticity of an Electrified Ionic Liquid/Electrode Interface: Uncovering Hard–Soft Structuring via Controlled Metal Fill Factor

Clarke, Osai J. R.; Rowley, Annabel; Fox, Robert V.; Burgess, Ian J.; Atifi, Abderrahman

doi:10.1021/acsnano.4c03617

Nano-Plasticity of an Electrified Ionic Liquid/Electrode Interface: Uncovering Hard–Soft Structuring via Controlled Metal Fill Factor

Journal Article · Wed May 22 00:00:00 EDT 2024 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.4c03617· OSTI ID:2396693

Clarke, Osai J. R. ^[1]; Rowley, Annabel ^[1]; ^[2]; ^[1]; ^[2]

Univ. of Saskatchewan, Saskatoon, SK (Canada)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Here, ionic liquids (ILs) nanostructuring at electrified interfaces is of both fundamental and practical interest as these materials are increasingly gaining prominence in energy storage and conversion processes. However, much remains unresolved about IL potential-controlled (re)organization under highly polarized interfaces, mostly due to the difficulty of selectively probing both the distal and proximal surface layers of adsorbed ions. In this work, the structural dynamics of the innermost layer (<10 nm from the surface) were independently interrogated from that of the ionic layers in the sub-surface region (>100 nm from the surface), using an infrared (IR) spectroscopy approach. By tuning the metal fill factor of gold films deposited on conductive metal oxide-modified IR internal reflection elements, the charge-driven (re)structuring of the inner and distal layers of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate is unveiled. Within a relatively wide potential region (~±1 V) bounding the potential of zero charges, the ionic liquid is shown to undergo a reversible (i.e., soft) reorganization whereby the innermost layer of anions (cations) is exchanged by a layer of cations (anions). Kinetically unhindered changes in the number density of constituent cations and anions largely follow electrostatic expectations in the subsurface region, whereas the innermost layer exhibits a pronounced hysteresis and very slow relaxation. Under larger negative potential bias, IL restructuring is characterized by a highly irreversible (i.e., hard) and intense interfacial densification of the BMPy⁺ cations, consistent with the formation of nanoscale segregated liquids. The outcomes of this work reveal a plastic IL nanostructuring under a strong electric field.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 2396693

Report Number(s):: INL/JOU-23-75673-Rev000

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 22 Vol. 18; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Nano-Plasticity of an Electrified Ionic Liquid/Electrode Interface: Uncovering Hard–Soft Structuring via Controlled Metal Fill Factor

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