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Confinement effects in microphase separated block copolymer electrolytes - conductivity and crystallinity.

Michael Patrick Blatt^1,2, Stephanie Posedel^1,2, Kyoungmin Kim^1,2

¹Department of Chemical and Biomedical Engineering, Florida A&M University-Florida State University (FAMU-FSU) College of Engineering, Tallahassee, FL 32310, USA. dhallinan@eng.famu.fsu.edu.

|November 17, 2025

Summary

Ionic conductivity in polymer electrolytes depends on morphology. Curvilinear morphologies enhance conductivity, while lamellar ones decrease it, offering insights for solid-state battery design.

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Area of Science:

Materials Science
Polymer Science
Electrochemistry

Background:

Block copolymers (BCPs) of polystyrene (PS) and poly(ethylene oxide) (PEO) are crucial for polymer electrolytes.
Understanding morphology's impact on ion transport is key for advanced battery technologies.

Purpose of the Study:

To investigate the influence of confinement and morphology on the ionic conductivity of PS-PEO block copolymer electrolytes.
To explore structure-property relationships for designing high-performance solid-state battery electrolytes.

Main Methods:

Synthesized and characterized PS-PEO block copolymers with spherical, cylindrical, and lamellar morphologies.
Prepared block copolymer electrolytes by incorporating lithium bis(trifluoromethanesulfonylimide) (LiTFSI) salt.
Measured domain spacing using X-ray scattering and defined a confinement length.

Main Results:

Confinement exponentially impedes PEO crystallization (exponential constant of 15 nm).
Ionic conductivity decreases with confinement in lamellar morphologies.
Curvilinear morphologies (spheres, cylinders) enhance conductivity as confinement increases.

Conclusions:

Morphology-dependent confinement significantly impacts ionic conductivity in PS-PEO electrolytes.
Curvilinear morphologies offer a promising route to enhanced ion transport for solid-state batteries.
These findings guide the rational design of advanced polymer electrolytes.