Since its discovery, polyaniline (PANI) has been a promising material for numerous applications due to its various desirable properties, e.g. tuneable conductivity, high pseudocapacitance or biocompatibility [1]. PANI has been incorporated as a composite for many electrochemical applications, from supercapacitors [2] to sensors [3], but its full potential is still limited by its poor processability as it cannot fully access the benefits of novel fabrication techniques like additive manufacturing (AM). The structural complexity and design flexibility of AM combined with the great properties of PANI would open up new application fields, from energy storage over wearable electronics to conductive implants. However, the non-thermoformable character of PANI limits the use of conventional AM techniques, e.g. Fused Deposition Modelling (FDM), to composites with only low PANI contents [4].Recently developed AM techniques using thermal doping of PANI [5] open up new possibilities for the use of PANI in AM. In this work, a novel process based on the thermal doping of PANI with dodecyl benzene sulfonic acid (DBSA) was used for the printing of electrodes for energy applications. For this, a commercially available FDM printer (Prusa i3 MK3S+) was modified with a 3D printed syringe extrusion system, replacing the regular print head. PANI emeraldine salt was synthesised using chemical oxidation and ultrasound at low temperatures, de-doped and ground to a small particle size. The polymer was then mixed with DBSA in order to obtain a viscous, printable paste. In this process, DBSA acts as both the dispersant and dopant for PANI. Thermal pre-treatment of the paste and the use of the printer hot-bed initiates the doping process, solidifying the paste, which allows for the AM of three dimensional conductive structures. The printing process was characterised and optimised in regards to pre-treatment time and temperature, hot bed temperature as well as nozzle distance from the hot bed. A fully 3D printed capacitor with PANI-DBSA electrodes and a polyvinyl alcohol/sulphuric acid electrolyte gel was fabricated and characterised in order to showcase the potential of this technique for electrochemical applications.[1] Baker, C. O., Huang, X., Nelson, W., Kaner, R. B., Chem Soc Rev 46 2581 (2001).[2]Shen, Y., Qin, Z., Li, T., Zeng, F., Chen, Y., Liu, N., Electrochimica Acta 356 136841 (2020).[3] Bao, Q., Yang, Z., Song, Y., Fan, M., Pan, P., Liu, J., Liao, Z., Wei, J., J. Mater. Sci.: Mater. Electron. 30 1751 (2018).[4] Wibowo, A., Vyas, C., Cooper, G., Qulub, F., Suratman, R., Mahyuddin, A. I., Dirgantara, T., Bartolo, P., Materials 13 512 (2020).[5] Holness, F., Price, A. D., Smart Mater. Struct. 1 015006 (2018).
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