Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes

Journal Article · 12 December 2019 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.9b01879 · OSTI ID:1658235

Morris, Melody A.  ^[1]; Sung, Seung Hyun  ^[1]; Ketkar, Priyanka M. ^[1]; Dura, Joseph A.  ^[2]; Nieuwendaal, Ryan C. ^[2]; Epps, III, Thomas H.  ^[1]

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1. University of Delaware, Newark, DE (United States)
2. National Institute of Standards and Technology (NIST), Gaithersburg, MD (United States)

The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-b-POEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (α > 1 state) promoted a “dry brush-like” homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations in the more mobile homopolymer-rich region, increasing overall ionic conductivity relative to the “wet brush-like” (α < 1 state) and unblended composites, where α is the molecular weight ratio between the POEM homopolymer and the POEM block in the copolymer. Here, neutron and X-ray reflectometry (NR and XRR, respectively) provided additional details on the lithium salt and polymer distributions. From XRR, the α > 1 blends showed increased interfacial widths in comparison to their BP (unblended) or α < 1 counterparts because of the more central distribution of the homopolymer. This result, paired with NR data that suggested even salt concentrations across the POEM domains, implied that there was a higher salt concentration in the homopolymer POEM-rich regions in the dry brush blend than in the wet brush blend. Furthermore, using ⁷Li solid-state nuclear magnetic resonance spectroscopy, we found a temperature corresponding to a transition in lithium mobility (T_{Li mobility}) that was a function of blend type. T_Li mobility was found to be 39 °C above T_g in all cases. Interestingly, the ionic conductivity of the blended BPs was highest in the α > 1 composites, even though these composites had higher T_gs than the α < 1 composites, demonstrating that homopolymer-rich conducting pathways formed in the α > 1 assemblies had a larger influence on conductivity than the greater lithium ion mobility in the α < 1 blends.

• Research Organization: Univ. of Delaware, Newark, DE (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
• Grant/Contract Number: SC0014458; DMR-1610134
• OSTI ID: 1658235
• Journal Information: Macromolecules, Vol. 52, Issue 24; ISSN 0024-9297
• Publisher: American Chemical SocietyCopyright Statement
• Country of Publication: United States
• Language: English