Charge state-dependent ion condensation near conjugated polymer backbones

Dilara Meli; Quentin Thomas; Nicolas Rolland; Guillaume Freychet; Christina J. Kousseff; Priscila Cavassin; Lucas Q. Flagg; Vincent Lemaur; Abhijith Surendran; Zeinab Hamid; Sophie Griggs; Ruiheng Wu; Rosalba A. Huerta; Isaiah D. Duplessis; Bryan D. Paulsen; Tobin J. Marks; Lincoln J. Lauhon; Iain McCulloch; Lee J. Richter; David Beljonne; Jonathan Rivnay

doi:10.1039/D5MH01939G

Charge state-dependent ion condensation near conjugated polymer backbones

Dilara Meli,

†^ab Quentin Thomas,

†^c Nicolas Rolland,

^cd Guillaume Freychet,^ef Christina J. Kousseff,

^g Priscila Cavassin,^b Lucas Q. Flagg,

^h Vincent Lemaur,

^c Abhijith Surendran,

ⁱ Zeinab Hamid,^g Sophie Griggs,^g Ruiheng Wu,‡^bj Rosalba A. Huerta,^ab Isaiah D. Duplessis,^ab Bryan D. Paulsen,

^ik Tobin J. Marks,

^abjl Lincoln J. Lauhon,

^ab Iain McCulloch,^gm Lee J. Richter,

^h David Beljonne^c and Jonathan Rivnay

*^abi

Author affiliations

* Corresponding authors

^a Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA
E-mail: jrivnay@northwestern.edu

^b Northwestern University Materials Research Center, Evanston, Illinois, USA

^c Laboratory for Chemistry of Novel Materials, Materials Research Institute, University of Mons, Mons, Belgium
E-mail: david.beljonne@umons.ac.be

^d Université de Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, F-59000 Lille, France

^e NSLS-II, Brookhaven National Laboratory, Upton, New York 11973, USA

^f Univ. Grenoble Alpes, CEA, Leti, F-38000 Grenoble, France

^g Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Oxford, UK

^h Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA

ⁱ Department of Biomedical Engineering, Northwestern University, Evanston, Illinois 60208, USA

^j Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA

^k Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN 46556, USA

^l Graduate Program in Applied Physics, Northwestern University, Evanston, Illinois 60208, USA

^m Andlinger Center for Energy and the Environment, Department of Electrical and Computer Engineering, Princeton University, Princeton, NJ 08544, USA

Abstract

Despite the technological appeal of polymeric organic mixed ionic/electronic conductors (OMIECs) for diverse applications, a deep understanding of the fundamentals of mixed charge transport in these materials, especially regarding the complex interplay between polymer, ion and solvent structure in determining transport, is lacking. Herein, extensive molecular dynamics (MD) simulations of a model OMIEC representing various electrochemically gated states are reported that reveal charge state-dependent counterion condensation. X-ray diffraction simulations based on the MD data predict a measurable change in the scattering intensity at the counterion absorption edge, indicative of counterion repositioning with charging. We leverage an operando resonant X-ray scattering technique to experimentally corroborate the simulated scattering and report excellent agreement between predicted and experimental data, confirming that counterions preferentially reside in the lamellar mid-plane of crystallites at low doping, and near the polymer backbone at higher doping. Driving forces for ion type-dependent spatial repositioning and implications thereof are discussed.

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Charge state-dependent ion condensation near conjugated polymer backbones

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