Emergent Nanostructure and Ion Transport in Polyzwitterion/Polyanion Blends

Li, Hongwei; Zhu, Qinyu; Shinohara, Yuya; Wang, Yangyang; Christakopoulos, Panagiotis; Kudlack, Autumn F.; Huang, Zitan; Bonnesen, Peter V.; Do, Changwoo; Rahman, Md Anisur; Lehmann, Michelle L.; Saito, Tomonori; Colby, Ralph H.; Kumar, Rajeev; Lutkenhaus, Jodie L.

doi:10.1021/acs.macromol.5c00806

Emergent Nanostructure and Ion Transport in Polyzwitterion/Polyanion Blends

Journal Article · Tue Aug 12 00:00:00 EDT 2025 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5c00806· OSTI ID:2587598

Li, Hongwei ^[1]; ^[2]; ^[3]; ^[2]; ^[2]; ^[1]; ^[4]; ^[2]; ^[3]; ^[3]; Lehmann, Michelle L. ^[3]; ^[3]; ^[4]; ^[2]; ^[1]

Texas A & M Univ., College Station, TX (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Pennsylvania State Univ., University Park, PA (United States)

Solid polymer electrolytes (SPEs) hold great promise for the advancement of next-generation energy storage devices. However, the ion transport mechanism in SPEs remains poorly understood. In this study, we investigate blends of poly(1-(3-sulfonatopropyl)-2-vinylpyridinium) (P2VPPS) and poly(lithium (trifluoromethane)sulfonimide methacrylate) (P(MTFSI)Li) of varying molar ratios to develop a mechanistic understanding of ionic conductivity in a miscible polyzwitterion/polyanion system. Polyanions can act as single-ion conductors, but conductivity is often prohibitively low due to the decreased segmental mobility and ion aggregation. Here, it is hypothesized that the introduction of a polyzwitterion would competitively interact with the polyanion charge groups to realize improvements in the conductivity. Attractive interactions between the polyanions and polyzwitterions are confirmed by the blend’s increased glass transition temperature using the Gordon–Taylor equation. Notably, an ordered local nanostructure (∼24 Å) emerged in the P2VPPS/P(MTFSI)Li system at certain compositions, as characterized by small-angle X-ray and neutron scattering (SAXS/SANS). Concurrent with the emergence of this structure, broadband dielectric spectroscopy confirmed improvements in ionic conductivity. The highest conductivity is observed at a specific blend ratio P2VPPS:P(MTFSI)Li = 0.2:1 in the glassy state and 0.3:1 in the rubbery state, corresponding to the lowest effective activation energy (E*). Coarse-grained molecular dynamics simulations further emphasize the role of complexation between polyzwitterion and polyanion chains, correlating with the emergence of a new peak in SAXS and SANS for the blends. This work provides a fresh perspective on the role of local structural design in developing SPEs and offers insights into the morphological effects on ionic conductivity.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Texas A&M University, College Station, TX (United States)

Sponsoring Organization:: National Energy Research Scientific Computing Center (NERSC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2587598

Alternate ID(s):: OSTI ID: 3002578

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 16 Vol. 58; ISSN 1520-5835; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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