Automated transfer of large-area defect-free graphene using a fluid transfer system

This invention is for scalable methods that allows preparation of bulk quantities of holey nanocarbons with holes ranging from a few to over 100 nm in diameter. The first method uses metal particles as a catalyst (silver, copper, e.g.) and offers a wider range of hole diameter. The second method is free of catalysts altogether and offers more rapid processing in a single step with minimal product work-up requirements and does not require solvents, catalysts, flammable gases, additional chemical agents, or electrolysis. The process requires only commercially available materials and standard laboratory equipment; and, it is scalable. Properties that can be controlled include: surface area, pore volume, mechanical properties, electrical conductivity, and thermal conductivity.

The HGM or composite HGM developed is a novel nanocarbon-based architecture that (1) is prepared from dry processing from commercially available starting materials or readily prepared composites thereof; (2) exhibits micropores and mesopores due to the holey graphene sheets and their stacking; (3) exhibits micron- and macro-sized pores in the article. The method can produce a range of high-fidelity hole size, shape, and distribution on the graphene or composite articles. The disclosed laser-based method is easily scaled-up and automatable. The result is a novel ultra-lightweight graphene-based mesh structure with high electrical conductivity, thermal conductivity, high surface area, high through-thickness unimpeded ion transport, mechanical robustness. The HGM-based composites utilize HGM as a novel framework, matrix, or substrate for secondary components that are active for energy storage, catalysis, sensing, optical, filtration, and biological applications.

In traditional batteries with liquid electrolytes, e.g., lithium-ion, each battery cell must be individually sealed, packaged, and electrically connected to other cells in the pack. The cells in solid-state batteries on the other hand may be stacked on top of one another with only a separation layer in between, called a bipolar plate. These bipolar plates or membranes if thin enough must be electrochemically inert to the electrode and electrolyte materials while providing electrical connectivity between the individual cells. Here, NASA has combined advances in the preparation of carbon nanomaterials and solid-state batteries to create extremely lightweight bipolar plates and membranes. These bipolar membranes will enable high energy density solid-state batteries unachievable with typical bipolar plate materials like stainless steel, aluminum, aluminum-copper, or conductive ceramics. The carbon bipolar membranes may be fabricated in multiple ways including but not limited to directly compressing carbon powders onto an electrode-electrolyte stack or separately making a film of the carbon material and dry pressing the film between other battery layers. The new bipolar membranes have been demonstrated in high energy density solid-state batteries in coin and pouch cells. The carbon bipolar membranes are at technology readiness level TRL-4 (Component and or breadboard validation in laboratory environment)and are available for patent licensing.

Various aerospace and terrestrial applications require lightweight materials with very high mechanical properties. Carbon nanotubes and graphene sheets have been found to be such materials. In addition, they have been found to have excellent electrical and thermal transport properties. However, retaining the excellent nanoscale properties, particularly mechanical and thermal transport, in bulk materials has proven to be challenging. In order for the nanotubes to be used in applications, they must be spun into yarn(s), sheet(s), and other macroscopic forms introducing relatively weak tube-to-tube and inter-bundle bonds. Also, the nanotubes tend to be entangled, and they therefore do not all contribute in load bearing. Weak coupling at tube and bundle interfaces also leads to mechanical and thermal transport that are much lower than would be expected from the nanoscale carbon nanotube or graphene properties. This invention is for consolidated carbon nanotube or graphene yarns and woven sheets via the formation of a carbon binder formed from the dehydration of sucrose. The resulting materials are lightweight and possess a high specific modulus and/or strength on the macro-scale. Sucrose is relatively inexpensive and readily available, leading to a cost-effective route for achieving bulk nanotube/graphene based multifunctional material formats.

The electrodes are soaked in electrolyte, separated by a separator membrane and packaged into a cell assembly to form an electrochemical double layer supercapacitor. Its capacitance can be enhanced by a redox capacitance contribution through additional metal oxide to the porous structure of vertical graphene or coating the vertical graphene with an electrically conducting polymer. Vertical graphene offers high surface area and porosity and does not necessarily have to be grown in a single layer and can consist of two to ten layers. A variety of collector metals can be used, such as silicon, nickel, titanium, copper, germanium, tungsten, tantalum, molybdenum, & stainless steel. Supercapacitors are superior to batteries in that they can provide high power density (in units of kw/kg) and the ability to charge and discharge in a matter of seconds. Aside from its excellent power density, a supercapacitor also has a longer life cycle and can undergo many more charging sequences in its lifespan than batteries. This long life cycle means that supercapacitors last for longer periods of times, which alleviates environmental concerns associated with the disposal of batteries.