Holey Carbon Allotropes

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.

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.

Fabrication of the biocapsule is accomplished by the use of a perforated mold, which allows CNTs in suspension or solution to be deposited by vacuum filtration. Other methods of creating a pressure differential between the outside of the mold and the inside of the mold can be used to drive the CNT deposition process. The mesh builds up gradually, over the course of minutes, so the thickness of the mesh can be controlled by the time of deposition. The fabrication procedure results in a mesh that is held together entirely by entanglement and non-covalent interaction between the CNTs. Filtration of CNTs onto the surface of a mold as the method of biocapsule fabrication is superior to other methods of fabrication that require assembly from multiple pieces of buckypaper, since these methods require seams in order to create a closed container. Seams result in weakness of the biocapsule and can result in leakage of the transplanted cells outside the container, which defeats the immune-shielding function of the biocapsule. The perforated mold/filtration method makes biocapsule manufacture more efficient, and makes possible a wider range of shapes of the biocapsule, to facilitate transplantation into a wider range of sites in the body. The perforated mold/filtration method also allows small beads to be incorporated into the wall of the biocapsule. Small beads, functionalized with bioactive materials, may be used to maintain the health or enhance the function of the cells inside the biocapsule, or may be used to enhance biocompatibility. The pores of the biocapsule permit gas exchange (oxygen, carbon dioxide), as well as free diffusion of metabolites, proteins and other cell products, which keep the cells healthy, and may provide useful therapeutics. Tissue or tissue fragments, and micro or nanoscale medical devices can also be placed inside the biocapsule to facilitate their implantation into the body.

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.

To protect the graphite (Gr)-based substrates in a nuclear systems fuel elements from hot hydrogen attacks, earlier researchers developed a method to deposit (via chemical vapor deposition) a protective niobium carbide (NbC) or zirconium carbide (ZrC) coating in the inner cooling channels of the fuel elements through which the hydrogen propellant flows. Unfortunately, the significant difference in the coefficients of thermal expansion (CTE) between the Gr-based substrate and the ZrC coating leads to debonding at intermediate temperatures, thereby exposing the substrate to hot hydrogen attack despite the NbC or ZrC coating. Innovators at Glenn have proposed a solution to this problem by introducing additional layers of compliant metallic coatings to accommodate the differences in CTE between the ZrC and the Gr-substrate,thereby potentially increasing life and durability. In this configuration,the innermost layer is composed of molybdenum carbide (Mo2C), and additional outer layers are made of molybdenum (Mo) and niobium (Nb) layers. The MoC acts as a diffusion barrier to minimize the diffusion of carbon into the refractory metal layers and the diffusion of Mo or Nb into the Gr-based substrate. The Mo layer is deposited on top of the Mo2C layer. A Nb layer is deposited on the Mo layer with the ZrC forming the outside layer of the coating. A thin Mo layer on the ZrC helps to seal the cracks on the ZrC and acts a diffusion barrier to hydrogen diffusion into the coating.The Mo and Nb layers are compliant so that differences in the thermal expansion of ZrC and other layers can be accommodated without significant debonding or cracking. They also act as additional diffusion barriers to hydrogen diffusion towards the Gr-substrate. Overall, Glenn's pioneering use of layered coatings for these components will potentially increase the durability and performance of nuclear propulsion rockets.