TY - JOUR
T1 - Decoupled Cation Transport within Layered Assemblies in Sulfonated and Crystalline Telechelic Polyethylenes
AU - Paren, Benjamin A.
AU - Häußler, Manuel
AU - Rathenow, Patrick
AU - Mecking, Stefan
AU - Winey, Karen I.
N1 - Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society and Division of Chemical Education, Inc.
PY - 2022/4/12
Y1 - 2022/4/12
N2 - We present a set of sulfonated monodisperse telechelic polyethylene ionomers that demonstrate ion transport of metal cations in layered ionic assemblies. These semicrystalline ionomers have precisely 48 backbone carbons with a sulfonated group at each end and are fully neutralized by a counterion, C48(SO3X)2 (X = Li+ or Na+). The morphology of these polymers is characterized by using X-ray scattering, and ionic conductivity is probed by using electrochemical impedance spectroscopy. These telechelic polyethylenes exhibit well-defined ionic layers at all temperatures below the melting point, and the crystal packing of the backbone varies with temperature. The polyethylene backbone packs in hexagonal crystals at high temperatures in both C48(SO3Li)2 and C48(SO3Na)2, with Arrhenius activation energies (Ea) for ion transport of 120 and 53 kJ mol-1, respectively, indicating that decoupled ion transport is possible through these layered ionic assemblies. The Ea in this hexagonal regime is significantly lower than Ea at room temperature where C48(SO3Li)2 exhibits disordered crystals and C48(SO3Na)2 exhibits orthorhombic crystallites, highlighting the impact of polymer packing between the ionic layers. At intermediate temperatures (120-160 °C) the hexagonal crystal structure in C48(SO3Na)2 coexists with an unidentified crystal phase that appears to have superior ion transport properties. When compared to other single ion conductors of the same functionality, C48(SO3Na)2 also demonstrates the importance of ionic assembly shape and identifies ionic layers as a promising strategy relative to assemblies with less order.
AB - We present a set of sulfonated monodisperse telechelic polyethylene ionomers that demonstrate ion transport of metal cations in layered ionic assemblies. These semicrystalline ionomers have precisely 48 backbone carbons with a sulfonated group at each end and are fully neutralized by a counterion, C48(SO3X)2 (X = Li+ or Na+). The morphology of these polymers is characterized by using X-ray scattering, and ionic conductivity is probed by using electrochemical impedance spectroscopy. These telechelic polyethylenes exhibit well-defined ionic layers at all temperatures below the melting point, and the crystal packing of the backbone varies with temperature. The polyethylene backbone packs in hexagonal crystals at high temperatures in both C48(SO3Li)2 and C48(SO3Na)2, with Arrhenius activation energies (Ea) for ion transport of 120 and 53 kJ mol-1, respectively, indicating that decoupled ion transport is possible through these layered ionic assemblies. The Ea in this hexagonal regime is significantly lower than Ea at room temperature where C48(SO3Li)2 exhibits disordered crystals and C48(SO3Na)2 exhibits orthorhombic crystallites, highlighting the impact of polymer packing between the ionic layers. At intermediate temperatures (120-160 °C) the hexagonal crystal structure in C48(SO3Na)2 coexists with an unidentified crystal phase that appears to have superior ion transport properties. When compared to other single ion conductors of the same functionality, C48(SO3Na)2 also demonstrates the importance of ionic assembly shape and identifies ionic layers as a promising strategy relative to assemblies with less order.
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U2 - 10.1021/acs.macromol.2c00132
DO - 10.1021/acs.macromol.2c00132
M3 - Article
AN - SCOPUS:85127165997
SN - 0024-9297
VL - 55
SP - 2813
EP - 2820
JO - Macromolecules
JF - Macromolecules
IS - 7
ER -