Electrochemistry of Thin Films with In Situ/Operando Grazing Incidence X-Ray Scattering: Bypassing Electrolyte Scattering for High Fidelity Time Resolved Studies

Bryan D. Paulsen, Alexander Giovannitti, Ruiheng Wu, Joseph Strzalka, Qingteng Zhang, Jonathan Rivnay*, Christopher J. Takacs*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

30 Scopus citations

Abstract

Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X-ray scattering is powerful for the characterization of stand-alone and ex situ organic thin films, in situ/operando structural characterization has been underutilized—in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, a new methodology for in situ/operando X-ray characterization that separates the incident and scattered X-ray beam path from the electrolyte is developed. As a proof of concept, the operando structural characterization of weakly-scattering, organic mixed conducting thin films in an aqueous electrolyte environment is demonstrated, accessing previously unexplored changes in the π-π peak and diffuse scatter, while capturing the solvent swollen thin film structure which is inaccessible in previous ex situ studies. These in situ/operando measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, new directions enabled by this in situ/operando cell design are examined and state of the art measurements are compared.

Original languageEnglish (US)
Article number2103213
JournalSmall
Volume17
Issue number42
DOIs
StatePublished - Oct 21 2021

Funding

B.D.P., R.W., and J.R. gratefully acknowledge support from the National Science Foundation Grant No. NSF DMR-1751308. A.G. acknowledges funding from the TomKat Center for Sustainable Energy at Stanford University. This research used resources of the Advanced Photon Source, (beamline 8-ID-E), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. This work made use of the Keck-II, NUFAB, and SPID facilities of Northwestern University's NUANCE Center, which received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern's MRSEC program (NSF DMR-1720139). This work made use of the MatCI Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. The authors thank to Carla Shute, Ross Arthur, Tim Dunn, Bart Johnson, Hans-Georg Steinrueck, Kevin Stone, Vivek Thampy, Chris Tassone, and Mike Toney for useful discussion; and Quentin Thiburce and Xudong Ji for assistance with the gold deposition. B.D.P., R.W., and J.R. gratefully acknowledge support from the National Science Foundation Grant No. NSF DMR‐1751308. A.G. acknowledges funding from the TomKat Center for Sustainable Energy at Stanford University. This research used resources of the Advanced Photon Source, (beamline 8‐ID‐E), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515. This work made use of the Keck‐II, NUFAB, and SPID facilities of Northwestern University's NUANCE Center, which received support from the SHyNE Resource (NSF ECCS‐2025633), the IIN, and Northwestern's MRSEC program (NSF DMR‐1720139). This work made use of the MatCI Facility supported by the MRSEC program of the National Science Foundation (DMR‐1720139) at the Materials Research Center of Northwestern University. The authors thank to Carla Shute, Ross Arthur, Tim Dunn, Bart Johnson, Hans‐Georg Steinrueck, Kevin Stone, Vivek Thampy, Chris Tassone, and Mike Toney for useful discussion; and Quentin Thiburce and Xudong Ji for assistance with the gold deposition.

Keywords

  • electrochemistry
  • grazing incidence wide-angle X-ray scattering
  • in situ
  • operando
  • organic mixed ionic-electronic conductors
  • polymers

ASJC Scopus subject areas

  • Engineering (miscellaneous)
  • General Chemistry
  • General Materials Science
  • Biotechnology
  • Biomaterials

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