Towards 3D-lithium ion microbatteries based on silicon/graphite blend anodes using a dispenser printing technique

In this work we present for the first time high capacity silicon/carbon-graphite blend slurries designed for application in 3D-printed lithium ion microbatteries (3D-MLIBs). The correlation between electrochemical and rheological properties of the corresponding slurries was systematically investigated with the prospect of production by an automated dispensing process. A variation of the binder content (carboxymethyl cellulose/styrene-butadiene rubber, CMC/SBR) between 6 wt%, 12 wt%, 18 wt% and 24 wt% in the anode slurry proved to be crucial for the printing process. Regarding the rheological properties increasing binder content leads to increased viscosity and yield stress values promising printed structures with high aspect ratios. Consequently, interdigital 3D-printed micro anode structures with increasing aspect ratios were printed with increasing binder content. For printed 6-layer structures aspect ratios of 6.5 were achieved with anode slurries containing 24 wt% binder. Electrochemical results from planar coin cell measurements showed that anodes containing 12 wt% CMC/SBR binder content exhibited stable cycling at the highest charge capacities of 484 mA h g-1 at a current rate of C/4. Furthermore, at 4C the cells showed high capacity retention of 89% compared to cycling at C/4. Based on this study and the given material formulation we recommend 18 wt% CMC/SBR as the best trade-off between electrochemical and rheological properties for future work with fully 3D-printed MLIBs.