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Lithium-salt-doped block copolymers have the potential to serve as solid electrolytes in rechargeable batteries with lithium metal anodes. In this work, we use small-angle X-ray scattering (SAXS) to study the structure of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) doped with bis-(trifluoromethylsulfonyl)amine lithium salt (LiTFSI) during direct current (dc) polarization experiments in lithium-lithium symmetric cells. The block copolymer studied is nearly symmetric in composition, has a total molecular weight of 39 kg mol-1, and exhibits a lamellar morphology at all studied salt concentrations. When ionic current is passed through the electrolyte, a salt concentration gradient forms that induces a spatial gradient in the domain spacing, d. The dependence of d on distance from the positive electrode, x, was determined experimentally by scanning the incident X-ray beam from one lithium electrode to the other. By studying the two-dimensional (2D) SAXS patterns as a function of azimuthal scattering angle, we find that lamellae with PS/PEO interfaces oriented perpendicular to the flow of ionic current (LAM∥) swell and contract to a greater degree than those with interfaces oriented parallel to the current direction (LAM||). While domains with the LAM∥ do not provide direct conducting pathways between the electrodes, our analysis suggests that they play an important role in establishing the salt concentration gradient necessary for sustaining a large ionic current through greater expansion and contraction.

Lithium-salt-doped block copolymers have the potential to serve as solid electrolytes in rechargeable batteries with lithium metal anodes. In this work, we use small-angle X-ray scattering (SAXS) to study the structure of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) doped with bis-(trifluoromethylsulfonyl)amine lithium salt (LiTFSI) during direct current (dc) polarization experiments in lithium-lithium symmetric cells. The block copolymer studied is nearly symmetric in composition, has a total molecular weight of 39 kg mol-1, and exhibits a lamellar morphology at all studied salt concentrations. When ionic current is passed through the electrolyte, a salt concentration gradient forms that induces a spatial gradient in the domain spacing, d. The dependence of d on distance from the positive electrode, x, was determined experimentally by scanning the incident X-ray beam from one lithium electrode to the other. By studying the two-dimensional (2D) SAXS patterns as a function of azimuthal scattering angle, we find that lamellae with PS/PEO interfaces oriented perpendicular to the flow of ionic current (LAM∥) swell and contract to a greater degree than those with interfaces oriented parallel to the current direction (LAM||). While domains with the LAM∥ do not provide direct conducting pathways between the electrodes, our analysis suggests that they play an important role in establishing the salt concentration gradient necessary for sustaining a large ionic current through greater expansion and contraction.