Influence of Extruder Setup and Process Parameters on the Product Quality of Solid Polymer Electrolytes Using Melt Extrusion

All solid-state batteries (ASSBs) are the next generation battery technology, in which the classical liquid electrolyte is replaced by an ion-conducting solid electrolyte. Materials that are used as solid-state electrolytes are generally divided into three material classes: polymers, oxides and sulphides. Electrolyte materials for ASSBs have been extensively studied regarding their electrochemical performance and their stability towards the electrode materials. Nevertheless, the commercialization of ASSBs is still hindered by the material availability in case of oxide and sulphides and the knowledge of scaled production routes for all kinds of separators. Polymers are readily available on the global market. It is thus possible to focus more on the processing routes of polymer based solid electrolytes. The use of thermoplastics as matrix for solid electrolytes (SE) offers the prospect of facile upscaling of the process from lab-scale to industrial series production by the implementation of a solvent-free thermal extrusion process. A twin-screw extruder offers the possibility of continuously mixing the SE components to produce homogeneous polymer based SEs. With two feeding units, the addition of the components takes place separately. This eliminates the time-consuming premixing step to obtain a homogeneous mixture. Thermoplastic poly(ethylene oxide) (PEO) is one of the most investigated materials for polymer based SEs due to its capability to dissolve alkali salts like Lithium(bistrifluoromethanesulfonyl)imide (LiTFSI). The thermal process route of PEO and its effect on the polymeric properties are currently under investigation. Previous works from our research group show that the processability of PEO not only depends on the conductive salt (LiTFSI), but also on its molecular weight and applied process parameters. [1] With increasing molecular weight, PEO becomes more sensitive towards thermal and mechanical load that leads to chain scissoring and degradation even at small load. Hence, the use of low molecular weight PEO (M w = 100.000 g mol -1 ) is preferable for the dry production of PEO based SEs. The aim of this work is to optimize the extrusion process using a co-rotating twin-screw extruder for the solvent free production of solid PEO/LiTFSI-electrolytes in a molar ratio of 20:1 (EO:Li). Here, we investigate the effects of several extruder set-ups on the mixing behaviour of PEO and LiTFSI. Therefore, type of dosing and screw design are varied. The screw can be designed with conveying, kneading and mixing elements. We compare the dry extrusion of a premixed PEO/LiTFSI (20:1) batch with dry extrusion of PEO/LiTFSI (20:1) using two feeding units, one for each component. Process parameters, such as pressure at the extruder die, actual screw speed, torque and barrel temperature are continuously measured during the production. Process temperature and screw speed are optimized to avoid degradation of PEO. PEO/LiTFSI-electrolytes are produced with a process temperature of 90 °C across the whole extruder barrel and with screw speeds of 5 – 15 rpm. The products are evaluated by their homogeneity and quality of the extruded electrolytes. Optical microscopy is used for macroscopic evaluation and the Li-salt distribution is checked with SEM/EDX. Conductivity and rheology measurements are performed to determine the lithium concentration within the electrolyte and loss of molecular weight, respectively. For the determination of the ionic conductivity, we examine electrochemical impedance spectroscopy (EIS). The characterization of the extruded electrolytes helps to find optimal process parameters for the production of polymer based SEs. References [1] K. Platen, F.Langer, R. Bayer, R. Hollmann, J. Schwenzel, M. Busse, Polymers 2023, 15, 3375.