Selective deposition of metal oxide nanoflakes on graphene electrodes to obtain high-performance asymmetric micro-supercapacitors.

To meet the charging market demands of portable microelectronics, there has been a growing interest in high performance and low-cost microscale energy storage devices with excellent flexibility and cycling durability. Herein, interdigitated all-solid-state flexible asymmetric micro-supercapacitors (A-MSCs) were fabricated by a facile pulse current deposition (PCD) approach. Mesoporous Fe2O3 and MnO2 nanoflakes were functionally coated by electrodeposition on inkjet-printed graphene patterns as negative and positive electrodes, respectively. Our PCD approach shows significantly improved adhesion of nanostructured metal oxide with crack-free and homogeneous features, as compared with other reported electrodeposition approaches. The as-fabricated Fe2O3/MnO2 A-MSCs deliver a high volumetric capacitance of 110.6 F cm-3 at 5 µA cm-2 with a broad operation potential range of 1.6 V in neutral LiCl/PVA solid electrolyte. Furthermore, our A-MSC devices show a long cycle life with a high capacitance retention of 95.7% after 10 000 cycles at 100 µA cm-2. Considering its low cost and potential scalability to industrial levels, our PCD technique could be an efficient approach for the fabrication of high-performance MSC devices in the future.

Facile fabrication of graphene-based high-performance microsupercapacitors operating at a high temperature of 150 °C.

Many industry applications require electronic circuits and systems to operate at high temperatures over 150 °C. Although planar microsupercapacitors (MSCs) have great potential for miniaturized on-chip integrated energy storage components, most of the present devices can only operate at low temperatures (<100 °C). In this work, we have demonstrated a facile process to fabricate activated graphene-based MSCs that can work at temperatures as high as 150 °C with high areal capacitance over 10 mF cm-2 and good cycling performance. Remarkably, the devices exhibit no capacitance degradation during temperature cycling between 25 °C and 150 °C, thanks to the thermal stability of the active components.

Drying-Mediated Self-Assembly of Graphene for Inkjet Printing of High-Rate Micro-supercapacitors.

Scalable fabrication of high-rate micro-supercapacitors (MSCs) is highly desired for on-chip integration of energy storage components. By virtue of the special self-assembly behavior of 2D materials during drying thin films of their liquid dispersion, a new inkjet printing technique of passivated graphene micro-flakes is developed to directly print MSCs with 3D networked porous microstructure. The presence of macroscale through-thickness pores provides fast ion transport pathways and improves the rate capability of the devices even with solid-state electrolytes. During multiple-pass printing, the porous microstructure effectively absorbs the successively printed inks, allowing full printing of 3D structured MSCs comprising multiple vertically stacked cycles of current collectors, electrodes, and sold-state electrolytes. The all-solid-state heterogeneous 3D MSCs exhibit excellent vertical scalability and high areal energy density and power density, evidently outperforming the MSCs fabricated through general printing techniques.

Fully inkjet printed ultrathin microsupercapacitors based on graphene electrodes and a nano-graphene oxide electrolyte.

The advance of miniaturized and low-power electronics has a striking impact on the development of energy storage devices with constantly tougher constraints in terms of form factor and performance. Microsupercapacitors (MSCs) are considered a potential solution to this problem, thanks to their compact device structure. Great efforts have been made to maximize their performance with new materials like graphene and to minimize their production cost with scalable fabrication processes. In this regard, we developed a full inkjet printing process for the production of all-graphene microsupercapacitors with electrodes based on electrochemically exfoliated graphene and an ultrathin solid-state electrolyte based on nano-graphene oxide. The devices exploit the high ionic conductivity of nano-graphene oxide coupled with the high electrical conductivity of graphene films, yielding areal capacitances of up to 313 µF cm-2 at 5 mV s-1 and high power densities of up to ∼4 mW cm-3 with an overall device thickness of only ∼1 µm.

Scalable Fabrication and Integration of Graphene Microsupercapacitors through Full Inkjet Printing.

A simple full-inkjet-printing technique is developed for the scalable fabrication of graphene-based microsupercapacitors (MSCs) on various substrates. High-performance graphene inks are formulated by integrating the electrochemically exfoliated graphene with a solvent exchange technique to reliably print graphene interdigitated electrodes with tunable geometry and thickness. Along with the printed polyelectrolyte, poly(4-styrenesulfonic acid), the fully printed graphene-based MSCs attain the highest areal capacitance of ∼0.7 mF/cm2, substantially advancing the state-of-art of all-solid-state MSCs with printed graphene electrodes. The full printing solution enables scalable fabrication of MSCs and effective connection of them in parallel and/or in series at various scales. Remarkably, more than 100 devices have been connected to form large-scale MSC arrays as power banks on both silicon wafers and Kapton. Without any extra protection or encapsulation, the MSC arrays can be reliably charged up to 12 V and retain the performance even 8 months after fabrication.

Inkjet printed highly transparent and flexible graphene micro-supercapacitors.

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.