Additive Manufacturing Assisted Solvent Casting of 3D Free-Standing Carbonaceous Hydrogels and Aerogels As Electrodes for Supercapacitors

Abstract

In a quest for renewable and highly efficient energy storage devices, carbonaceous hydrogels obtained from biopolymers have received much attention owing to their multifunctional properties [1]. The ability to fine-tune the structures of these hydrogels and the prospects of fabricating 3D hydrogels-based carbon electrodes with highly porous and interconnected nanostructure is believed to provide efficient migration of electrolyte ions and electrons. Even though additive manufacturing (AM) of hydrogels with 3D structures could simplify the fabrication, the printability of each material varies greatly. Furthermore, the mechanical properties of hydrogels are often too weak to withstand the printing of structures with a certain height [2].Herein, we demonstrate a facile and versatile method for the fabrication of novel and highly porous 3D carbon aerogel electrodes from bio-hydrogels based on additive manufacturing assisted solvent casting process followed by freeze drying and pyrolysis. Firstly, the negative templates with the required resolution and geometry were 3D printed using high-resolution stereolithography (SLA) based AM technology to be used as master molds and the pattern were transferred to the biopolymeric hydrogels during ionic crosslinking induced self-assembly, leading to gelation. After completion of the gelling process, the casted hydrogel was removed from the master mold, washed with deionized water, frozen using solid carbon dioxide (dry ice) and lyophilized (freeze-dried) to preserve the structure. The lyophilized free-standing aerogels were then converted to free-standing 3D pyrolytic carbon aerogels in a high-temperature tubular furnace at 900°C under a nitrogen environment. Different characterization techniques such as FTIR, BET, SEM, Raman, XRD and XPS were employed to access the influence of the process parameters on the final microstructure of the 3D carbon aerogels. The as-prepared 3D free-standing carbon aerogel when used as a binder-free electrode showed outstanding charge storage capability and kinetics arising from interconnected 3D porous channels. The versatility of this approach was further verified by the successful preparation of novel multifunctional 3D free-standing carbon aerogel hybrids using GO, CNT and/or metal oxides and its application as a structured binder-free supercapacitor electrode with improved electrochemical performance.With the advantageous features of synergistically regulating the structure and composition, the proposed method combining AM and casting could be used as a versatile tool to develop structured bio-hydrogels, to be used as precursor material for constructing novel architectured free-standing carbon electrode materials with well-defined geometry and controlled pore size distribution. The final shape of carbon electrode depends on the 3D geometry of the additive manufactured negative template used for the replication during solvent casting. This technique would broaden the library of hydrogels materials that could be constructed freely in three-dimensions for the fabrication of structured and free-standing porous bio-carbon based electrodes for high-performance supercapacitor application.