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

doi:10.1002/smll.202103213

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

Biomedical Engineering

Research output: Contribution to journal › Article › peer-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 language	English (US)
Article number	2103213
Journal	Small
Volume	17
Issue number	42
DOIs	https://doi.org/10.1002/smll.202103213
State	Published - 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

Access to Document

10.1002/smll.202103213

Cite this

@article{27eed76553e24ff3929a281e58a1d804,

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

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.",

keywords = "electrochemistry, grazing incidence wide-angle X-ray scattering, in situ, operando, organic mixed ionic-electronic conductors, polymers",

author = "Paulsen, {Bryan D.} and Alexander Giovannitti and Ruiheng Wu and Joseph Strzalka and Qingteng Zhang and Jonathan Rivnay and Takacs, {Christopher J.}",

note = "Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = oct,

day = "21",

doi = "10.1002/smll.202103213",

language = "English (US)",

volume = "17",

journal = "Small",

issn = "1613-6810",

publisher = "Wiley-VCH Verlag",

number = "42",

}

TY - JOUR

T1 - Electrochemistry of Thin Films with In Situ/Operando Grazing Incidence X-Ray Scattering

T2 - Bypassing Electrolyte Scattering for High Fidelity Time Resolved Studies

AU - Paulsen, Bryan D.

AU - Giovannitti, Alexander

AU - Wu, Ruiheng

AU - Strzalka, Joseph

AU - Zhang, Qingteng

AU - Rivnay, Jonathan

AU - Takacs, Christopher J.

PY - 2021/10/21

Y1 - 2021/10/21

N2 - 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.

AB - 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.

KW - electrochemistry

KW - grazing incidence wide-angle X-ray scattering

KW - in situ

KW - operando

KW - organic mixed ionic-electronic conductors

KW - polymers

UR - http://www.scopus.com/inward/record.url?scp=85115252423&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85115252423&partnerID=8YFLogxK

U2 - 10.1002/smll.202103213

DO - 10.1002/smll.202103213

M3 - Article

C2 - 34549509

AN - SCOPUS:85115252423

SN - 1613-6810

VL - 17

JO - Small

JF - Small

IS - 42

M1 - 2103213

ER -

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

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this