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  1. Abstract

    Single‐ion conducting polymer electrolytes are of interest for use with advanced battery electrodes such as lithium metal, but achieving sufficiently high conductivity has been challenging. In this work, a model system containing charged sites that are precisely spaced along the polymer backbone is explored. Precision sulfonated poly(4‐phenylcyclopentene) lithium salt (p5PhS‐Li) with a high degree of sulfonation (> 90%) is synthesized and blended with poly(ethylene oxide) (PEO) to investigate the thermodynamic and transport properties. Melting point depression is measured via differential scanning calorimetry, ionic conductivity,κ, is determined using electrochemical impedance spectroscopy, and the fraction of current carried by Li+is estimated based on steady‐state current measurements. In conjunction with a density measurement, melting point depression is used to find an effective Flory–Huggins interaction parameter,χeff=   − 0.21, suggesting miscibility of the blend.κspans a large range from 2 × 10−11to 2 × 10−7S cm−1over the composition and temperature range investigated. The fraction of charge carried by lithium ions also spans a significant range from 0.12 in majority PEO blend to 0.98 in majorityp5PhS‐Li blend. This study addresses several limitations of sulfonated polystyrene and opens up the possibility of precisely controlling the spacing of other anion types.

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  2. Abstract

    Lignin is an aromatic‐rich biomass polymer that is cheap, abundant, and sustainable. However, its application in the solid electrolyte field is rare due to challenges in well‐defined polymer synthesis. Herein, the synthesis of lignin‐graft‐poly(ethylene glycol) (PEG) and its conductivity test for a solid electrolyte application are demonstrated. The main steps of synthesis include functionalization of natural lignin's hydroxyl to alkene, followed by graft‐copolymerization of PEG thiol to the lignin via photoredox thiol‐ene reaction. Two lignin‐graft‐PEGs are prepared having 22 wt% lignin (lignin‐graft‐PEG 550) and 34 wt% lignin (lignin‐graft‐PEG 2000). Then, new polymer electrolytes for conductivity tests are prepared via addition of lithium bis‐trifluoromethanesulfonimide. The polymer graft electrolytes exhibit ionic conductivity up to 1.4 × 10−4 S cm−1 at 35 °C. The presence of lignin moderately impacts conductivity at elevated temperature compared to homopolymer PEG. Furthermore, the ionic conductivity of lignin‐graft‐PEG at ambient temperature is significantly higher than homopolymer PEG precedents.

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  3. A novel precision single-ion conductor with phenylsulfonyl(trifluoromethylsulfonyl)imide lithium salt covalently bound to every fifth carbon of a polyethylene backbone, p5PhTFSI-Li, was synthesized via ring opening metathesis polymerization (ROMP) followed by post polymerization modification. The conversion of poly(4-phenylcyclopentene), bearing 94% sulfonate anions, to trifluoromethanesulfonimide (TFSI) anions was highly efficient (∼90%) as determined by 19 F NMR analysis and corroborated through other spectroscopic methods. The flexible hydrocarbon backbone combined with a bulky TFSI anion led to an observable glass transition temperature of 199 °C even at these high levels of ionization. A high thermal stability up to 375 °C was also observed. Blending of p5PhTFSI-Li with poly(ethylene oxide) at various compositions was performed to investigate electrochemical performance and transference numbers with respect to the lithium electrode using a combination of impedance and polarization methods. At 90 °C and a 50 : 50 wt% blend composition, this system displayed the highest reported conductivity (2.00 × 10 −4 S cm −1 ) of a system with a demonstrated lithium-ion transference number near unity. Such performance is also atypical of single ion conductors produced through post-polymerization modification, which we attribute to the high yield of TFSI conversion. Investigations into the complex miscibility and phase behavior of these blends at various compositions was also probed by a combination of microscopy and differential scanning calorimetry, which is discussed with reference to computational predictions of how charge correlations affect polymer blend phase behavior. 
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  4. Hydrolytic degradation of commercially available 3D printing filament, i.e. poly (lactic acid) with broad molecular weight distribution was induced by incubating 3D-printed parts in deionized water at 3 temperatures. Small changes in orthogonal dimensions occurred due to relaxation of printing stresses, but no mass or volume loss were detected over the time-frame of the experiments. Molecular weight decreased while polydispersity remained constant. The most sensitive measure of degradation was found to be nondestructive, small-amplitude oscillatory tensile measurements. A rapid decay of tensile storage modulus was found with an exponential decay time constant of about an hour. This work demonstrates that practical monitoring of commercially available PLA degradation can be achieve with linear viscoelastic measurements of modulus. 
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  5. null (Ed.)