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    In situ preparation of crosslinked polymer electrolytes for lithium ion batteries
    (Basel : MDPI, 2020) Röchow, Eike T.; Coeler, Matthias; Pospiech, Doris; Kobsch, Oliver; Mechtaeva, Elizaveta; Vogel, Roland; Voit, Brigitte; Nikolowski, Kristian; Wolter, Mareike
    Solid polymer electrolytes for bipolar lithium ion batteries requiring electrochemical stability of 4.5 V vs. Li/Li+ are presented. Thus, imidazolium-containing poly(ionic liquid) (PIL) networks were prepared by crosslinking UV-photopolymerization in an in situ approach (i.e., to allow preparation directly on the electrodes used). The crosslinks in the network improve the mechanical stability of the samples, as indicated by the free-standing nature of the materials and temperature-dependent rheology measurements. The averaged mesh size calculated from rheologoical measurements varied between 1.66 nm with 10 mol% crosslinker and 4.35 nm without crosslinker. The chemical structure of the ionic liquid (IL) monomers in the network was varied to achieve the highest possible ionic conductivity. The systematic variation in three series with a number of new IL monomers offers a direct comparison of samples obtained under comparable conditions. The ionic conductivity of generation II and III PIL networks was improved by three orders of magnitude, to the range of 7.1 × 10−6 S·cm−1 at 20 °C and 2.3 × 10−4 S·cm−1 at 80 °C, compared to known poly(vinylimidazolium·TFSI) materials (generation I). The transition from linear homopolymers to networks reduces the ionic conductivity by about one order of magnitude, but allows free-standing films instead of sticky materials. The PIL networks have a much higher voltage stability than PEO with the same amount and type of conducting salt, lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). GII-PIL networks are electrochemically stable up to a potential of 4.7 V vs. Li/Li+, which is crucial for a potential application as a solid electrolyte. Cycling (cyclovoltammetry and lithium plating-stripping) experiments revealed that it is possible to conduct lithium ions through the GII-polymer networks at low currents. We concluded that the synthesized PIL networks represent suitable candidates for solid-state electrolytes in lithium ion batteries or solid-state batteries.
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    Direction dependent electrical conductivity of polymer/carbon filler composites
    (Basel : MDPI, 2019) Kunz, Karina; Krause, Beate; Kretzschmar, Bernd; Juhasz, Levente; Kobsch, Oliver; Jenschke, Wolfgang; Ullrich, Mathias; Pötschke, Petra
    The method of measuring electrical volume resistivity in different directions was applied to characterize the filler orientation in melt mixed polymer composites containing different carbon fillers. For this purpose, various kinds of fillers with different geometries and aspect ratios were selected, namely carbon black (CB), graphite (G) and expanded graphite (EG), branched multiwalled carbon nanotubes (b-MWCNTs), non-branched multiwalled carbon nanotubes (MWCNTs), and single-walled carbon nanotubes (SWCNTs). As it is well known that the shaping process also plays an important role in the achieved electrical properties, this study compares results for compression molded plates with random filler orientations in the plane as well as extruded films, which have, moreover, conductivity differences between extrusion direction and perpendicular to the plane. Additionally, the polymer matrix type (poly (vinylidene fluoride) (PVDF), acrylonitrile butadiene styrene (ABS), polyamide 6 (PA6)) and filler concentration were varied. For the electrical measurements, a device able to measure the electrical conductivity in two directions was developed and constructed. The filler orientation was analyzed using the ratio σin/th calculated as in-plane conductivity σin-plane (σin) divided by through-plane conductivity σthrough-plane (σth). The ratio σin/th is expected to increase with more pronounced filler orientation in the processing direction. In the extruded films, alignment within the plane was assigned by dividing the in-plane conductivity in the extrusion direction (x) by the in-plane conductivity perpendicular to the extrusion direction (y). The conductivity ratios depend on filler type and concentration and are higher the higher the filler aspect ratio and the closer the filler content is to the percolation concentration.