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Within the fields of materials science, producing reliable, long-lasting, and efficient energy storage devices to meet the world’s energy needs remains a foremost research goal. 3D-printing (also known as Additive Manufacturing) provides many benefits to this research 1-8, allowing for excellent customization and freedom of design, while eliminating waste material in the manufacturing process. Wearable electronics, medical implants, and the Internet of Things will doubtless benefit from the advantages provided by additive manufacturing. Our previous work compared the electrochemical performances of symmetric carbon-based supercapacitor devices made using two 3D-printing techniques, SLA (stereolithography) and FDM (fused deposition modelling). Though possessing excellent cycle life, the conductive polylactic acid (PLA) FDM printed current collectors suffered from relatively high resistance and poor cyclic voltammetry curves (far from the rectangular shape of ideal electronic double-layer capacitors). This study aims to improve the conductivity of the FDM current collectors via chemically induced surface modification 9. Both dimethylformamide (DMF) and aqueous potassium hydroxide (KOH) treatments are used for this purpose. The untreated, DMF-treated, and KOH-treated FDM current collectors are loaded with 1:1 by mass single-walled carbon nanotubes and graphene nanoplatelets carbon slurry, placed within stereolithography (SLA) 3D-printed casings 10, and assembled as supercapacitor cells (separated by glass microfiber filter separators soaked in 6 M aqueous KOH electrolyte). This works shows how DMF treatment method results in little change in electrochemical performance compared to the untreated FDM current collector cells, but pre-treatment in a solution of KOH identical to the cell electrolyte markedly improves the current collector conductivity. The KOH treatment provides a tenfold decrease in the FDM current collector resistance, which correlates with the improved cyclic voltammetric response. Galvanostatic charge-discharge tests reveal the effect of these treatments on specific capacitance, charge-discharge response, efficiency, and rate capability for these printed cells. The pre-treatment confirms that the cell electrolyte does not limited long term performance by interacting with the PLA current collector in 3D printed supercapacitor cells and tests using other inorganic active materials will also be shown. References 1 A. Ambrosi and M. Pumera, "3D-printing technologies for electrochemical applications.," Chemical society reviews, vol. 45, no. 10, pp. 2740-2755, 2016. 2 V. Egorov and C. O'Dwyer, "Architected porous metals in electrochemical energy storage.," Current Opinion in Electrochemistry, vol. 21, pp. 201-208, 2020. 3 V. Egorov, U. Gulzar, Y. Zhang, S. Breen and C. O'Dwyer, "Evolution of 3D printing methods and materials for electrochemical energy storage.," Advanced Materials, vol. 32, no. 29, p. 2000556, 2020. 4 U. Gulzar, C. Glynn and C. O'Dwyer, "Additive manufacturing for energy storage: Methods, designs and material selection for customizable 3D printed batteries and supercapacitors.," Current Opinion in Electrochemistry, vol. 20, pp. 46-53, 2020. 5 J. Li, M. Leu, R. Panat and J. Park, "A hybrid three-dimensionally structured electrode for lithium-ion batteries via 3D printing.," Materials & Design, vol. 119, pp. 417-424, 2017. 6 A. Maurel, M. Courty, B. Fleutot, H. Tortajada, K. Pdrashantha, M. Armand, S. Grugeon, S. Panier and L. Dupont, "Highly loaded graphite–polylactic acid composite-based filaments for lithium-ion battery three-dimensional printing.," Chemistry of Materials, vol. 30, no. 21, pp. 7484-7493, 2018. 7 S. O'Hanlon and C. O'Dwyer, "Electrodeposition onto Conductive Additive-Impregnated 3D Printed Polylactic Acid Electrodes.," Journal of The Electrochemical Society, vol. 169, no. 8, p. 082514, 2022. 8 B. Yao, S. Chandrasekaran, J. Zhang, W. Xiao, F. Qian, C. Zhu, E. Duoss, C. Spadaccini, M. Worsley and Y. Li, "Efficient 3D printed pseudocapacitive electrodes with ultrahigh MnO2 loading.," Joule, vol. 3, no. 2, pp. 459-470, 2019. 9 S. Srinivasan K. V, J. Santo and P. Penumakala, "Effect of surface modification of printed electrodes on the performance of supercapacitors," Journal of Energy Storage, vol. 56, no. B, p. 106043, 2022. 10 U. Gulzar, V. Egorov, Y. Zhang, and C. O’Dwyer, "Recyclable 3D-Printed Aqueous Lithium-Ion Battery", Adv. Energy Sustainability Res. 4, 2300029, 2023.
Ferguson et al. (Fri,) studied this question.