The Influence of 3D Printing Methods and Materials on the Response of Printed Symmetric Carbon Supercapacitors

We compare the electrochemical response and intrinsic limitations of symmetric carbon-based supercapacitors using two 3D-printing techniques, vat polymerization (Vat-P) and fused deposition modelling (FDM). Two cell types were made in this study, one with metallized Vat-P-printed current collectors, the other with PLA (polylactic acid) FDM-printed current collectors in a similarly designed printed coin cell. Carbon-based electrode slurry (various combinations of SWCNT, GNP, Super-P, PVDF) and aqueous 6 M KOH electrolyte were used in these cells. We demonstrate the influence of internal resistance of each 3D-printing method by direct comparison of cyclic voltammetry and galvanostatic charge-discharge tests. The metallized conductive Vat-P cells display better conductivity and more ideal rectangular cyclic voltammetry response but suffer from poor cycle life in initial experiments (∼5,000 charge-discharge cycles before losing all specific capacitance). The FDM current collector cells using graphite-containing PLA materials have poorer conductivity, less ideal cyclic voltammetry curves, and are structurally less robust and partially porous, but offer very stable cycle life for supercapacitor cells retaining most of their specific capacitance after 100,000 charge-discharge cycles. The cycle life of the metallized Vat-P cells are improved by reducing the voltage window to 0.2-0.7 V to limit metal delamination and using Super-P and PVDF additives.