TY - JOUR
T1 - Quantitative Composition and Mesoscale Ion Distribution in p-Type Organic Mixed Ionic-Electronic Conductors
AU - Wu, Ruiheng
AU - Paulsen, Bryan D.
AU - Ma, Qing
AU - McCulloch, Iain
AU - Rivnay, Jonathan
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/6/28
Y1 - 2023/6/28
N2 - Understanding the ionic composition and distribution in organic mixed ionic-electronic conductors (OMIECs) is crucial for understanding their structure-property relationships. Despite this, direct measurements of OMIEC ionic composition and distribution are not common. In this work, we investigated the ionic composition and mesoscopic structure of three typical p-type OMIEC materials: an ethylene glycol-treated crosslinked OMIEC with a large excess fixed anionic charge (EG/GOPS-PEDOT:PSS), an acid-treated OMIEC with a tunable fixed anionic charge (crys-PEDOT:PSS), and a single-component OMIEC without any fixed anionic charge (pg2T-TT). A combination of X-ray fluorescence (XRF) and X-ray photoelectron spectroscopies, gravimetry, coulometry, and grazing incidence small-angle X-ray scattering (GISAXS) techniques was employed to characterize these OMIECs following electrolyte exposure and electrochemical cycling. In particular, XRF provided quantitative ion-to-monomer compositions for these OMIECs from passive ion uptake following aqueous electrolyte exposure and potential-driven ion uptake/expulsion following electrochemical doping and dedoping. Single-ion (cation) transport in EG/GOPS-PEDOT:PSS due to Donnan exclusion was directly confirmed, while significant fixed anion concentrations in crys-PEDOT:PSS doping and dedoping were shown to occur through mixed anion and cation transport. Controlling the fixed anionic (PSS-) charge density in crys-PEDOT:PSS mapped the strength of Donnan exclusion in OMIEC systems following a Donnan-Gibbs model. Anion transport dominated pg2T-TT doping and dedoping, but a surprising degree of anionic charge trapping (∼1020 cm-3) was observed. GISAXS revealed minimal ion segregation both between PEDOT- and PSS-rich domains in EG/GOPS-PEDOT:PSS and between amorphous and semicrystalline domains in pg2T-TT but showed significant ion segregation in crys-PEDOT:PSS at length scales of tens of nm, ascribed to inter-nanofibril void space. These results bring new clarity to the ionic composition and distribution of OMIECs which are crucial for accurately connecting the structure and properties of these materials.
AB - Understanding the ionic composition and distribution in organic mixed ionic-electronic conductors (OMIECs) is crucial for understanding their structure-property relationships. Despite this, direct measurements of OMIEC ionic composition and distribution are not common. In this work, we investigated the ionic composition and mesoscopic structure of three typical p-type OMIEC materials: an ethylene glycol-treated crosslinked OMIEC with a large excess fixed anionic charge (EG/GOPS-PEDOT:PSS), an acid-treated OMIEC with a tunable fixed anionic charge (crys-PEDOT:PSS), and a single-component OMIEC without any fixed anionic charge (pg2T-TT). A combination of X-ray fluorescence (XRF) and X-ray photoelectron spectroscopies, gravimetry, coulometry, and grazing incidence small-angle X-ray scattering (GISAXS) techniques was employed to characterize these OMIECs following electrolyte exposure and electrochemical cycling. In particular, XRF provided quantitative ion-to-monomer compositions for these OMIECs from passive ion uptake following aqueous electrolyte exposure and potential-driven ion uptake/expulsion following electrochemical doping and dedoping. Single-ion (cation) transport in EG/GOPS-PEDOT:PSS due to Donnan exclusion was directly confirmed, while significant fixed anion concentrations in crys-PEDOT:PSS doping and dedoping were shown to occur through mixed anion and cation transport. Controlling the fixed anionic (PSS-) charge density in crys-PEDOT:PSS mapped the strength of Donnan exclusion in OMIEC systems following a Donnan-Gibbs model. Anion transport dominated pg2T-TT doping and dedoping, but a surprising degree of anionic charge trapping (∼1020 cm-3) was observed. GISAXS revealed minimal ion segregation both between PEDOT- and PSS-rich domains in EG/GOPS-PEDOT:PSS and between amorphous and semicrystalline domains in pg2T-TT but showed significant ion segregation in crys-PEDOT:PSS at length scales of tens of nm, ascribed to inter-nanofibril void space. These results bring new clarity to the ionic composition and distribution of OMIECs which are crucial for accurately connecting the structure and properties of these materials.
KW - Donnan−Gibbs model
KW - ion composition
KW - organic mixed ionic-electronic conductors
KW - X-ray fluorescence
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U2 - 10.1021/acsami.3c04449
DO - 10.1021/acsami.3c04449
M3 - Article
C2 - 37326843
AN - SCOPUS:85164211728
SN - 1944-8244
VL - 15
SP - 30553
EP - 30566
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 25
ER -