Modern energy storage devices for portable and wearable technologies must fulfill a number of requirements, such as small size, flexibility, thinness, reliability, transparency, manufacturing simplicity and performance, in order to be competitive in an ever expanding market. To this end, a comprehensive inkjet printing process is developed for the scalable and low-cost fabrication of transparent and flexible micro-supercapacitors. These solid-state devices, with printed thin films of graphene flakes as interdigitated electrodes, exhibit excellent performance versus transparency (ranging from a single-electrode areal capacitance of 16 μF cm⁻² at transmittance of 90% to a capacitance of 99 μF cm⁻² at transmittance of 71%). Also, transparent and flexible devices are fabricated, showing negligible capacitance degradation during bending. The ease of manufacturing coupled with their great capacitive properties opens up new potential applications for energy storage devices ranging from portable solar cells to wearable sensors.

Graphene is a promising electrode material for supercapacitors mainly because of its large specific surface area and high conductivity. In practice, however, several fabrication issues need refinement. The restacking of graphene flakes upon being packed into supercapacitor electrodes has become a critical challenge in the full utilization of graphene’s large specific surface area to further improve the device performance. In this review, a variety of recent techniques and strategies are overviewed for the prevention of graphene restacking. They have been classified into several categories to improve and facilitate the discussion on the underlying ideas. Based on the overview of the existing techniques, we discuss the trends of future research in the fields.

On‐paper microsupercapacitors (MSCs) are a key energy storage component for disposable electronics that are anticipated to essentially address the increasing global concern of electronic waste. However, nearly none of the present on‐paper MSCs combine eco‐friendliness with high electrochemical performance (especially the rate capacity). In this work, highly reliable conductive inks based on the ternary composite of poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS), graphene quantum dots and graphene are developed for scalable inkjet printing of compact (footprint area ≈ 20 mm²) disposable MSCs on commercial paper substrates. Without any post treatment, the printed patterns attain a sheet resistance as low as 4 Ω ▫⁻¹. The metal‐free all‐solid‐state MSCs exhibit a maximum areal capacitance > 2 mF cm⁻² at a high scan rate of 1000 mV s⁻¹, long cycle life (>95% capacitance retention after 10 000 cycles), excellent flexibility, and long service time. Remarkably, the “totally metal‐free” MSC arrays are fully inkjet printed on paper substrates and also exhibit high rate performance. The life cycle assessment indicates that these printed devices have much lower eco‐toxicity and global warming potential than other on‐paper MSCs.