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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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6 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Modifying Li + and Anion Diffusivities in Polyacetal Electrolytes: A Pulsed-Field-Gradient NMR Study of Ion Self-Diffusion

Polyacetal electrolytes have been demonstrated as promising alternatives to liquid electrolytes and poly(ethylene oxide) (PEO) for rechargeable lithium-ion batteries; however, the relationship between polymer structure and ion motion is difficult to characterize. Here, we study structure-property trends in ion diffusion with respect to polymer composition for a systematic series of five polyacetals with varying ratios of ethylene oxide (EO) to methylene oxide (MO) units, denoted as P(xEO-yMO), and PEO. We first use 7 Li and 19 F pulsed-field-gradient NMR spectroscopy to measure cation and anion self-diffusion, respectively, in polymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixtures. At 90 °C, we observe modest changes in Li + diffusivity across all polymer compositions, while anion (TFSI - ) self-diffusion coefficients decrease significantly with increasing MO content. At a given reduced temperature (T - T g ), all polyacetal electrolytes exhibit faster Li + self-diffusion than PEO. Intriguingly, P(EO-MO) and P(EO-2MO) also show slower TFSI - anion self-diffusion than PEO at a given reduced temperature. Molecular dynamics simulations reveal that shorter distances between acetal oxygen atoms (O-CH 2 -O) compared to ether oxygens (O-CH 2 -CH 2 -O) promote more diverse, often asymmetric, Li + coordination environments. Finally, Raman spectra reveal that anion-rich ion clusters in P(EO-MO) and P(EO-2MO) lead to decreased anion diffusivity, which along with increased cation diffusivity, support the viability of polyacetals as high-performance polymer electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Improved Li + Transport in Polyacetal Electrolytes: Conductivity and Current Fraction in a Series of Polymers

Polymer electrolytes mitigate safety concerns surrounding flammable liquid electrolytes in lithium-ion batteries. Poly(ethylene oxide) (PEO) electrolytes demonstrate viable conductivity values (~1 × 10 -3 S/cm) at elevated temperatures (>70 °C) but a relatively low Li + current fraction (≤0.2) because strong Li + coordination inhibits cation mobility. We have developed a series of polyacetal electrolytes by systematically varying methylene oxide (MO) and ethylene oxide (EO) units in the polymer backbone. These materials maintain high oxygen-to-carbon ratios like PEO but offer improved ion transport, revealing trends of decreasing conductivity and increasing current fraction with respect to polymer composition. In particular, the increasing current fraction measured via the Bruce-Vincent method suggests that MO units improve Li+ mobility relative to anion mobility. Here, we calculate an overall efficacy (product of conductivity and current fraction) for each polymer/salt composition and identify two polymers - P(EO-MO) and P(EO-2MO) - that outperform PEO at high and low salt concentrations, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exploring the Ion Solvation Environments in Solid-State Polymer Electrolytes through Free-Energy Sampling

The success of poly(ethylene oxide) (PEO) in solid-state polymer electrolytes for lithium-ion batteries is well established. Recently, in order to understand this success and to explore possible alternatives, we studied polyacetal electrolytes to deepen the understanding of the effect of the local chemical structure on ion transport. Advanced molecular dynamics techniques using newly developed, tailored interaction potentials have helped elucidate the various coordination environments of ions in these systems. In particular, the competition between cation-Anion pairing and coordination by the polymer has been explored using free-energy sampling (metadynamics). At equivalent reduced temperatures, with respect to the polymer-specific glass-Transition temperature, two-dimensional free-energy plots reveal the existence of multiple coordination environments for the lithium (Li) ions in these systems and their relative stabilities. Furthermore, we observe that the Li-ion movement in PEO follows a serial, stepwise pathway when moving from one coordination state to another, whereas this happens in a more continuous and concerted fashion in a polyacetal such as poly(1,3-dioxalane) [P(EO-MO)]. The implication is that interconversion between coordination states of the Li ions may be easier in P(EO-MO). However, the overarching observation from our free-energy analysis is that Li-ion coordination is dominated by the polymer (in either case) and contact-ion pairs are rare. We rationalize the observed higher increase in glass-Transition temperature (Tg) with salt loading in polyacetals as due to intermolecular Li-ion coordination involving multiple polymer chains, rather than just one chain for PEO-based electrolytes. This interchain coupling in the polyacetals, resulting in the higher Tg, works against any gains due to variations in Li-ion coordination that might enhance transport processes over PEO. Further research is required to overcome the interdependence between local coordination and macroscopic properties to compete with PEO electrolytes at the same absolute working temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing to the low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP of cyclic acetals using a commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, we synthesize poly(1,3-dioxolane) (PDXL), which demonstrates tensile strength comparable to some commodity polyolefins. Depolymerization of PDXL using strong acid catalysts returns monomer in near-quantitative yield and even proceeds from a commodity plastic waste mixture. Our efficient polymerization method affords a tough thermoplastic that can undergo selective depolymerization to monomer.

Abel, Brooks A.↗
NASA NTRS1993

Applications of fibrous substrates containing insolubilized phase change polymers

Incorporation of polyethylene glycols into fibrous substrates produces several improved functional properties when they are insolubilized by crosslinking with a methylolamide resin or by polyacetal formation by their reaction with glyoxal. The range of molecular weights of polyols that may be insolubilized is broad as are the curing conditions (0.25-10 min at 80-200C). Most representative fiber types and blends (natural and synthetic) and all types of fabric constructions (woven, nonwoven and knit) have been modified by incorporation of the bound polyols. The most novel property is the thermal adaptability of the modified substrates to many climatic conditions. This adaptability is due to the high latent heat of the crosslinked polyols that function as phase change materials, the hydrophilic nature of the crosslinked polymer and its enhanced thermal conductivity. Other enhanced properties imparted to fabrics include flex and flat abrasion, antimicrobial activity, reduced static charge, resistance to oily soils, resiliency, wind resistance and reduced lint loss. Applications commercialized in the U.S. and Japan include sportswear and skiwear. Several examples of electric sets of properties useful for specific end uses are given. In addition, other uses are biomedical horticultural, aerospace, indoor insulation, automotive interiors and components and packaging material.

Vigo, Tyrone L.↗