Printing technologies are becoming increasingly popular because they enable the large-scale and low-cost production of functional devices with various designs, functions, mechanical properties and materials. Among these technologies, inkjet printing is promising thanks to its direct (mask-free) patterning, non-contact nature, low material waste, resolution down to 10 µm, and compatibility with a broad range of materials and substrates. As a result, inkjet printing has applications in several fields like wearables, opto-electronics, thin-film transistors, displays, photovoltaic devices, and in energy storage. It's in energy storage that the technique shows its full potential by allowing the production of miniaturized devices with a compact form factor, high power density and long cycle life, called microsupercapacitors (MSCs). To this end, graphene has a number of remarkable properties like high electrical conductivity, large surface area, elasticity and transparency, making it a top candidate as an electrode material for MSCs.

Some key drawbacks limit the use of inkjet printing for the production of graphene-based MSCs. This thesis aims at improving its scalability by producing fully inkjet printed devices, and extending its applications through the integration of inkjet printing with other fabrication techniques.

MSCs typically rely on the deposition by hand of gel electrolyte that is not printable or by submerging the whole structure into liquid electrolyte. Because of this, so far large-scale production of more than 10 interconnected devices has not been attempted. In this thesis, a printable gel electrolyte ink based on poly(4-styrene sulfonic acid) was developed, allowing the production of large arrays of more than 100 fully inkjet printed devices connected in series and parallel that can be reliably charged up to 12 V. Also, a second electrolyte ink based on nano-graphene oxide, a solid-state material with high ionic conductivity, was formulated to optimize the volumetric performance of these devices. The resulting MSCs were also fully inkjet printed and exhibited an overall device thickness of around 1 µm, yielding a power density of 80 mW cm^-3.

Next, the use of inkjet printing of graphene was explored for the fabrication of transparent MSCs. This application is typically hindered by the so-called coffee-ring effect, which creates dark deposits on the edges of the drying patterns and depletes material from the inside area. In light of this issue, inkjet printing was combined with etching to remove the dark deposits thus leaving uniform and thin films of graphene with vertical sidewalls. The resulting devices showed a transmittance of up to 90%.

Finally, the issue of the substrate compatibility of inkjet printed graphene was addressed. Although inkjet printing is considered to have broad substrate versatility, it is unreliable on hydrophilic or porous substrates and most inks (including graphene inks) require thermal annealing that damages substrates that are not resistant to heat. Accordingly, a technique based on inkjet printing and wet transfer was developed to reliably deposit graphene-based MSCs on a number of substrates, including flat, 3D, porous, plastics and biological (plants and fruits) with adverse surfaces.

The contributions of this thesis have the potential to boost the use of inkjet printed MSCs in applications requiring scalability and resolution (e.g. on-chip integration) as well as applications requiring conformability and versatility (e.g. wearable electronics).