Crowding and Anomalous Capacitance at an Electrode–Ionic Liquid Interface Observed Using Operando X-ray Scattering

Chu, Miaoqi; Miller, Mitchell; Dutta, Pulak

doi:10.1021/acscentsci.6b00014

Title: Crowding and Anomalous Capacitance at an Electrode–Ionic Liquid Interface Observed Using Operando X-ray Scattering

Journal Article · Mon Mar 07 00:00:00 EST 2016 · ACS Central Science

DOI:https://doi.org/10.1021/acscentsci.6b00014· OSTI ID:1240469

Chu, Miaoqi ^[1]; Miller, Mitchell ^[1]; Dutta, Pulak ^[1]

Department of Physics & Astronomy, Northwestern University, Evanston, Illinois 60208, United States

Room temperature ionic liquids are widely recognized as novel electrolytes with properties very different from those of aqueous solutions, and thus with many potential applications, but observing how they actually behave at electrolytic interfaces has proved to be challenging. We have studied the voltage-dependent structure of [TDTHP]⁺[NTF2]^- near its interface with an electrode, using in situ synchrotron X-ray reflectivity. An anion-rich layer develops at the interface above a threshold voltage of +1.75 V, and the layer thickness increases rapidly with voltage, reaching ~6 nm (much larger that the anion dimensions) at +2.64 V. Our results provide direct confirmation of the theoretical prediction of “crowding” of ions near the interface. The interfacial layer is not purely anionic but a mixture of up to ~80% anions and the rest cations. Moreover, the static differential capacitance calculated from X-ray measurements shows an increase at higher voltages, consistent with a recent zero-frequency capacitance measurement but inconsistent with ac capacitance measurements.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1240469

Alternate ID(s):: OSTI ID: 1243121

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Vol. 2 Journal Issue: 3; ISSN 2374-7943

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 37 works

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