No abstract

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.

A hermetic dense polymer-carbon composite-based current collector foil (PCCF) for lithium-ion battery applications was developed and evaluated in comparison to state-of-the-art aluminum (Al) foil collector. Water-processed LiNi0.5Mn1.5O4 (LMNO) cathode and Li4Ti5O12 (LTO) anode coatings with the integration of a thin carbon primer at the interface to the collector were prepared. Despite the fact that the laboratory manufactured PCCF shows a much higher film thickness of 55 µm compared to Al foil of 19 µm, the electrode resistance was measured to be by a factor of 5 lower compared to the Al collector, which was attributed to the low contact resistance between PCCF, carbon primer and electrode microstructure. The PCCF-C-primer collector shows a sufficient voltage stability up to 5 V vs. Li/Li+ and a negligible Li-intercalation loss into the carbon primer. Electrochemical cell tests demonstrate the applicability of the developed PCCF for LMNO and LTO electrodes, with no disadvantage compared to state-of-the-art Al collector. Due to a 50% lower material density, the lightweight and hermetic dense PCCF polymer collector offers the possibility to significantly decrease the mass loading of the collector in battery cells, which can be of special interest for bipolar battery architectures.

In the present study, melt-mixed composites based of poly (vinylidene fluoride) (PVDF) and fillers with different aspect ratios (carbon nanotubes (CNTs), carbon black (CB)) and their mixtures in composites were investigated whereby compression-molded plates were compared with melt-extruded films. The processing-related orientation of CNTs with a high aspect ratio leads to direction-dependent electrical and mechanical properties, which can be reduced by using mixed filler systems with the low aspect ratio CB. An upscaling of melt mixing from small scale to laboratory scale was carried out. From extruded materials, films were prepared down to a thickness of 50 µm by cast film extrusion under variation of the processing parameters. By combining CB and CNTs in PVDF, especially the electrical conductivity through the film could be increased compared to PVDF/CNT composites due to additional contact points in the sample thickness. The alignment of the fillers in the two directions within the films was deduced from the differences in electrical and mechanical film properties, which showed higher values in the extrusion direction than perpendicular to it.