Detection of the Order-to-Disorder Transition in Block Copolymer Electrolytes Using Quadrupolar <sup>7</sup>Li NMR Splitting

Grundy, Lorena S.; Sethi, Gurmukh K.; Galluzzo, Michael D.; Loo, Whitney S.; Maslyn, Jacqueline A.; Teran, Alexander A.; Thelen, Jacob L.; Timachova, Ksenia; Reimer, Jeffrey A.; Madsen, Louis A.; Balsara, Nitash P.

doi:10.1021/acsmacrolett.8b00809

Cited by 3 publications

(3 citation statements)

References 38 publications

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“…Furthermore, a non-zero 〈𝜒̅ 〉 indicates that there is an underlying preferred orientation of the environments of the bound states, consistent with the pancake structures of the PEDOT-rich regions. Similar small residual quadrupole coupling constants have previously been reported for liquid crystals 36 , co-polymers 37 , and hydrated biological samples 38 , in cases where local orderings are present. The zero value of 〈𝜒̅ 〉 observed for Na + in the PSS-regions, or indeed in the PSS-only films, indicates that the SO 3moieties (in these regions) are oriented randomly with respect to the magnetic field.…”

Section: Discussionsupporting

confidence: 86%

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

et al. 2023

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While organic mixed ionic/electronic conductors are widely studied for various applications in bioelectronics, energy generation/storage, and neuromorphic computing, a fundamental understanding of the interactions between the ionic and electronic carriers remains unclear, particularly in the wet state and on electrochemical cycling. Here, we show that operando NMR spectroscopy can selectively probe and quantify ion and water movement during the doping/dedoping of poly(3,4-ethylene dioxythiophene) poly(styrene sulfonate) (PEDOT:PSS) films, the most widely used organic mixed conductor. Na + ions near or within the PEDOT-rich domains experience an anisotropic environment resulting from the underlying partial PSS chain orientation in the polymer films, giving rise to a distinct quadrupolar splitting in the 23 Na NMR spectrum. Operando 23 Na NMR studies reveal a linear correlation between the quadrupolar splitting and the charge stored in the film, which is interpreted in terms of the roles that the Na + ions at the PEDOT/PSS interfaces play in charge balance and electric double layer formation. The observed correlation is quantitatively explained by a competitive binding model, in which holes on the PEDOT backbone are bound to PSS, the hole concentration changes during doping/dedoping inducing variations in the Na + binding percentage at the PEDOT/PSS interfaces. The Na + -to-electron coupling efficiency, measured via 23 Na NMR intensity changes, varies noticeably depending on the cycling history of the film. Operando 1 H NMR spectroscopy confirms that water molecules accompany the ions that are injected into/extracted from the films. These findings shed light on the working principles of organic mixed conductors and demonstrate the utility of operando NMR spectroscopy in revealing structure-property relationships in electroactive polymers.

show abstract

Section: Discussionsupporting

confidence: 86%

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

et al. 2023

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show abstract

“…Furthermore, a non-zero 〈 ̅ 〉 indicates that there is an underlying preferred orientation of the environments of the bound states, consistent with the pancake structures of the PEDOT-rich regions. Similar small residual quadrupole coupling constants have previously been reported for liquid crystals 36 , co-polymers 37 , and hydrated biological samples 38 , in cases where local orderings are present. The zero value of 〈 ̅ 〉 observed for Na + in the PSS-regions, or indeed in the PSS-only films, indicates that the SO 3moieties (in these regions) are oriented randomly with respect to the magnetic field.…”

Section: Discussionsupporting

confidence: 86%

Operando NMR Visualization of Ion Dynamics in PEDOT:PSS

Jin

Magusin

Sturniolo

et al. 2021

Preprint

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While organic mixed ionic/electronic conductors are widely studied for various applications in bioelectronics, energy generation/storage, and neuromorphic computing, a fundamental understanding of the interactions between the ionic and electronic carriers remains unclear, particularly in the wet state and on electrochemical cycling. Here, we show that operando NMR spectroscopy can selectively probe and quantify ion and water movement during the doping/dedoping of poly(3,4-ethylene dioxythiophene) poly(styrene sulfonate) (PEDOT:PSS) films, the most widely used organic mixed conductor. Na+ ions near or within the PEDOT-rich domains experience an anisotropic environment resulting from the underlying partial PSS chain orientation in the polymer films, giving rise to a distinct quadrupolar splitting in the 23Na NMR spectrum. Operando 23Na NMR studies reveal a linear correlation between the quadrupolar splitting and the charge stored in the film, which is interpreted in terms of the roles that the Na+ ions at the PEDOT/PSS interfaces play in charge balance and electric double layer formation. The observed correlation is quantitatively explained by a competitive binding model, in which holes on the PEDOT backbone are bound to PSS, the hole concentration changes during doping/dedoping inducing variations in the Na+ binding percentage at the PEDOT/PSS interfaces. The Na+-to-electron coupling efficiency, measured via 23Na NMR intensity changes, varies noticeably depending on the cycling history of the film. Operando 1H NMR spectroscopy confirms that water molecules accompany the ions that are injected into/extracted from the films. These findings shed light on the working principles of organic mixed conductors and demonstrate the utility of operando NMR spectroscopy in revealing structure-property relationships in electroactive polymers.

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“…The scattering vectors with similar ratios could also be calculated from WAXS in Figure B, indicating that the nanofibers were packing with columnar hexagonal lattice. To further verify the anisotropy of OPA LC phase, its alignment was demonstrated by deuterium ( 2 H) NMR. , In a 600 MHz 1 H NMR spectrometer, the deuterium resonance of DMSO- d 6 in the LC phase (10 wt %) exhibited a residual quadrupolar coupling (RQC) splitting of 76 Hz, indicating the excellent orientation of the self-assembled nanofibers. Intriguingly, the positive correlation between the RQC value and OPA concentration was observed (Figure C), suggesting the adjustable alignment degree of LC phase.…”

Section: Results and Discussionmentioning

confidence: 99%

A Lyotropic Liquid Crystal from a Flexible Oligopeptide Amphiphile in Dimethyl Sulfoxide

Ding

Liu

Qin

et al. 2020

ACS Appl. Bio Mater.

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Despite the rapid progress in peptide liquid crystals (LCs) due to their prominent properties, our investigation on flexible peptide-based LCs is incomplete, mainly resulted from their unclear formation mechanisms and unexploited applications in organic solvents. Here, we develop a lyotropic LC based on a flexible oligopeptide amphiphile, which aggregates into aligned cylinder-like nanostructures in dimethyl sulfoxide (DMSO). The formation mechanism of lyotropic LC in DMSO was probed by the experimental investigation and molecular dynamics simulation, indicating that the hydrogen bonding and hydrophobic and electrostatic interactions contribute to the formation of ordered nanostructures in the organic solvent. Arising from the orientational order and suitable fluidity, we exploit the application of lyotropic LC as an aligned medium to measure the residual dipolar couplings of bioactive molecules. This study not only offers the understanding of the mechanism to create LC systems without rigid aromatic groups but also expands the applications of ordered bottom-up nanomaterials in organic solvents.

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Detection of the Order-to-Disorder Transition in Block Copolymer Electrolytes Using Quadrupolar ⁷Li NMR Splitting

Cited by 3 publications

References 38 publications

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

Operando NMR Visualization of Ion Dynamics in PEDOT:PSS

A Lyotropic Liquid Crystal from a Flexible Oligopeptide Amphiphile in Dimethyl Sulfoxide

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Detection of the Order-to-Disorder Transition in Block Copolymer Electrolytes Using Quadrupolar 7Li NMR Splitting

Cited by 3 publications

References 38 publications

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

Operando NMR Visualization of Ion Dynamics in PEDOT:PSS

A Lyotropic Liquid Crystal from a Flexible Oligopeptide Amphiphile in Dimethyl Sulfoxide

Contact Info

Product

Resources

About

Detection of the Order-to-Disorder Transition in Block Copolymer Electrolytes Using Quadrupolar ⁷Li NMR Splitting