Chain Conformations of TEMPO-Based Organic Radical Polymers with Varying Radical Loading and Temperature in Battery-Relevant Solvents

Haque, Md Ashraful; Easley, Alexandra D.; Moncada, Josh G.; Lutkenhaus, Jodie L.; Dadmun, Mark D.

doi:10.1021/acs.macromol.4c01134

Chain Conformations of TEMPO-Based Organic Radical Polymers with Varying Radical Loading and Temperature in Battery-Relevant Solvents

Journal Article · Tue Jun 25 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c01134· OSTI ID:2552942

Haque, Md Ashraful ^[1]; Easley, Alexandra D. ^[2]; Moncada, Josh G. ^[1]; ^[2]; ^[1]

University of Tennessee, Knoxville, TN (United States)
Texas A&M University, College Station, TX (United States)

Poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) is an organic radical polymer that is a promising active material in organic batteries. The proximity of the radical groups impacts the nature of charge transfer, in which closer packing promotes electron exchange; however, the chain conformation of PTMA is not well understood. Here, the conformation of PTMA in, and its thermodynamic interactions with, battery-relevant solvents is determined using small-angle neutron scattering (SANS). N-methyl-2-pyrrolidone (NMP) and 50:50 (wt %) ethylene carbonate/dimethyl carbonate (EC/DMC) mixtures with PTMA of varying radical content (68 vs 98%) and temperature (25 and 60 °C) are examined. Both solvents are theta solvents for PTMA irrespective of radical loading and temperature. PTMA attains an expanded chain conformation in NMP and a more compact polymer chain conformation in EC/DMC. Lastly, the electrochemical performance of PTMA films formed from EC/DMC shows improved performance relative to those cast from NMP, which is interpreted to indicate that the compact conformation of PTMA in EC/DMC enables improved inter- and intrachain charge transfer.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve University, Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation Graduate Research Fellowship

Grant/Contract Number:: SC0019409; SC0014006

OSTI ID:: 2552942

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 13 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Chain Conformations of TEMPO-Based Organic Radical Polymers with Varying Radical Loading and Temperature in Battery-Relevant Solvents

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