Calcium-ion batteries emerged as a potential sustainable alternative energy storage system; however, there remains the need to further develop electrolytes to improve their performance. We report a gel polymer electrolyte (GPE)-based on polyvinylidene fluoride (PVDF) for calcium ion conduction. The gel electrolyte was synthesized by combining a PVDF polymer host, Ca(TFSI)2 salt, and N-methyl-2-pyrrolidone (NMP) solvent. Using Fourier transform infrared spectroscopy, we analyze the effect of salt concentration and drying temperature on the degree of salt dissociation in the electrolyte. Our results show that the concentration of free cations in the electrolyte is primarily coordinated with NMP as well as PVDF, generating a suitable network for ion transport, i.e., a liquid electrolyte encompassed within a polymer matrix. We find that processing conditions such as drying temperature, which varies solvent content, play a critical role in developing polymer electrolytes that demonstrate optimal electrochemical performance. The GPEs are semicrystalline and stable up to 120 °C, which is critical for their use in applications such as in electric vehicles and renewable energy storage systems. The ionic conductivity of the GPEs exhibit Arrhenius-type behavior, and the total ionic conductivity at room temperature is suitable for applications, with values of 0.85 × 10–4 S/cm for 0.5 M and 3.56 × 10–4 S/cm for 1.0 M concentrations. The results indicate that the GPE exhibits high conductivity and good stability, making it a promising candidate for use in high-performance calcium ion batteries.
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Promoting water-splitting in Janus bipolar ion-exchange resin wafers for electrodeionization
Electrochemical separation processes are undergoing a renaissance as the range of applications continues to expand because they offer opportunities for increased energy efficiency and sustainability in comparison to conventional separation technologies. Existing platforms such as electrodialysis and electrodeionization (EDI) are seeing significant improvement and are currently being deployed for treating a diverse set of liquid streams ( e.g. , water and wastewater treatment, organic acid separation, etc. ). In addition, the relatively low inherent electricity requirement for electrochemical separations could potentially be satisfied through integration with sustainable sources of renewable energy. In order to achieve a truly sustainable electrochemical separations process, it is paramount to improve the energy efficiency of electrochemical separations by minimizing all sources of resistances within these units. This work reports of a new class of symmetric and asymmetric Janus bipolar resin wafers (RWs) that augment the spacer channel ionic conductivity in EDI while having the additional functionality of splitting water into protons and hydroxide ions. The latter attribute is important in niche applications that require pH modulation such as silica and organic acid removal from liquid streams. The Janus bipolar RWs were devised from single ion-conducting RWs that were interfaced together to create an intimate polycation–polyanion junction. Interestingly, the conductivity of the single ion-conducting RWs at low salt concentrations was observed to be dependent on the ionic mobilities of the counterions that the RW was transferring. Using single ion-conducting RWs to construct Janus bipolar RWs enabled the incorporation of a water-splitting catalyst (aluminum hydroxide nanoparticles) into the porous ion-exchange resin bed. To the best of our knowledge, this is the first time a water dissociation catalyst has been implemented in the ion-exchange resin bed for EDI. The water dissociation catalyst in bipolar junctions pre-polarizes water making it easier to split into hydronium and hydroxide ion charge carriers under applied electric fields via the second Wien effect. The new molecularly layered Janus RWs demonstrate both satisfactory water-splitting and salt removal in bench scale EDI setups and these materials may improve, or even supplant, existing bipolar membrane electrodialysis units that currently necessitate large electrolyte feed concentrations.
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- Award ID(s):
- 1703307
- NSF-PAR ID:
- 10140453
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- ISSN:
- 2058-9689
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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 (
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Decavanadate (V 10 O 28 6− or V10) is a paradigmatic member of the polyoxidometalate (POM) family, which has been attracting much attention within both materials/inorganic and biomedical communities due to its unique structural and electrochemical properties. In this work we explored the utility of high-resolution electrospray ionization (ESI) mass spectrometry (MS) and ion exclusion chromatography LC/MS for structural analysis of V10 species in aqueous solutions. While ESI generates abundant molecular ions representing the intact V10 species, their isotopic distributions show significant deviations from the theoretical ones. A combination of high-resolution MS measurements and hydrogen/deuterium exchange allows these deviations to be investigated and interpreted as a result of partial reduction of V10. While the redox processes are known to occur in the ESI interface and influence the oxidation state of redox-active analytes, the LC/MS measurements using ion exclusion chromatography provide unequivocal evidence that the mixed-valence V10 species exist in solution, as extracted ion chromatograms representing V10 molecular ions at different oxidation states exhibit distinct elution profiles. The spontaneous reduction of V10 in solution is seen even in the presence of hydrogen peroxide and has not been previously observed. The susceptibility to reduction of V10 is likely to be shared by other redox active POMs. In addition to the molecular V10 ions, a high-abundance ionic signal for a V 10 O 26 2− anion was displayed in the negative-ion ESI mass spectra. None of the V 10 O 26 cations were detected in ESI MS, and only a low-abundance signal was observed for V 10 O 26 anions with a single negative charge, indicating that the presence of abundant V 10 O 26 2− anions in ESI MS reflects gas-phase instability of V 10 O 28 anions carrying two charges. The gas-phase origin of the V 10 O 26 2− anion was confirmed in tandem MS measurements, where mild collisional activation was applied to V10 molecular ions with an even number of hydrogen atoms (H 4 V 10 O 28 2− ), resulting in a facile loss of H 2 O molecules and giving rise to V 10 O 26 2− as the lowest-mass fragment ion. Water loss was also observed for V 10 O 28 anions carrying an odd number of hydrogen atoms ( e.g. , H 5 V 10 O 28 − ), followed by a less efficient and incomplete removal of an OH˙ radical, giving rise to both HV 10 O 26 − and V 10 O 25 − fragment ions. Importantly, at least one hydrogen atom was required for ion fragmentation in the gas phase, as no further dissociation was observed for any hydrogen-free V10 ionic species. The presented workflow allows a distinction to be readily made between the spectral features revealing the presence of non-canonical POM species in the bulk solution from those that arise due to physical and chemical processes occurring in the ESI interface and/or the gas phase.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9ME00179D
