Patent Application
20140178289
Individual graphene sheets have attracted significant attention since their isolation (Novoselov et al., Science 306, 666 (2004)), due to the multitude of graphene's exceptional properties (Gomez-Navarro et al., Nano Letters 7, 3499 (2007); Geim et al., Nature Materials 6, 183 (2007); Lee et al., Science 321, 385 (2008); Miller et al., Science 329, 1637 (2010); Novoselov et al., Science 315, 1379 (2007); Schedin et al., Nature Materials 6, 652 (2007); Zhu et al., Adv Mater 22, 3906 (2010); Chen et al., Nat Nano 3, 206 (2008).
Some of the properties observed in this nanoscale, two-dimensional (2D) form of graphitic carbon include room-temperature electrical conductivities up to ˜106 S/cm and Young's moduli up to ˜106 MPa, which are among the highest reported for any material. In an effort to realize the properties of individual graphene sheets on the macro-scale, several groups have recently developed three dimensional (3D) graphene assemblies with many promising characteristics.
Such assemblies are comprised of randomly interconnected graphene sheets with a large degree of porosity (>90%), which is believed to be necessary to minimize restacking of graphene sheets. These low-density nanoporous graphene structures exhibit electrical conductivities and Young's moduli as many as 10 orders of magnitude lower than those observed for individual graphene sheets, which is not surprising given their high porosity. It is a direct consequence of superlinear dependences of electrical and mechanical properties on the monolith density for porous materials.
Macro-scale 3D graphene-based materials exhibiting the exceptional properties, including combinations of properties, of graphene sheets are still a challenge. For example, electrical conductivity might be too low.
Embodiments provided herein include compositions, devices, and articles, as well as methods of making and methods of using the compositions, devices, and articles.
One embodiment provides for a composition comprising at least one high-density graphene-based monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds and having a density of at least 0.2 g/cm3.
Another embodiment provides a method comprising: preparing a reaction mixture comprising a suspension and at least one catalyst, said suspension selected from a graphene oxide (GO) suspension and a carbon nanotube suspension; curing the reaction mixture to produce a wet gel; drying the wet gel to produce a dry gel, said drying step is substantially free of supercritical drying and freezing drying; and pyrolyzing the dry gel to produce a high-density graphene-based monolith or a high-density carbon-nanotube-based monolith.
Another embodiment provides for a device comprising at least one high-density graphene-based monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds and having a density of at least 0.2 g/cm3.
Another embodiment provides for a composition comprising at least one high-density carbon-nanotube-based monolith, said monolith comprising carbon nanotubes crosslinked by nanoparticles and having a density of at least 0.2 g/cm3.
Another embodiment provides a method comprising: preparing a reaction mixture comprising a suspension and at least one catalyst, said suspension selected from a graphene oxide (GO) suspension and/or a carbon nanotube suspension; curing the reaction mixture to produce a wet gel; drying the wet gel to produce a dry gel without application of heat to raise the temperature beyond ambient temperature; and pyrolyzing the dry gel to produce a high-density graphene-based monolith or a high-density carbon-nanotube-based monolith.
At least one advantage for at least one embodiment is that bulk properties, such as Young's moduli, compressive strength, and electrical conductivity, can exceed those of commercial graphite at nearly half the density. Isotropic properties can approach those of graphene sheets. Another advantage for at least one embodiment is low annealing temperature.
References cited herein can be used to practice and better understand the claimed inventions and are incorporated by reference herein in their entireties for all purposes.
Priority U.S. provisional application Ser. No. 61/745,528 filed Dec. 21, 2012 is hereby incorporated by reference in its entirety for all purposes including working examples and claims.
US Patent Publication 2012/0034442 to Worsley et al., “Mechanically Stiff, Electrically Conductive Composites of Polymers and Carbon Nanotubes” is incorporated herein by reference in its entirety.
US Patent Publication 2010/0187484 to Worsley et al., “MECHANICALLY ROBUST, ELECTRICALLY CONDUCTIVE ULTRALOW-DENSITY CARBON NANOTUBE-BASED AEROGELS” is incorporated herein by reference in its entirety.
The article, “Mechanically Robust 3D Graphene Macroassembly with High Surface Area,” Worsley et al., Chem. Commun., 2012, 48, 8428-8430, is incorporated herein by reference in its entirety.
The article, “Synthesis of Graphene Aerogel with High Electrical Conductivity,” Worsley et al., J. Am. Chem. Soc., 2011, 2, 921-925, is incorporated herein by reference in its entirety.
The article, “High Surface Area, sp2-Cross-Linked Three-Dimensional Graphene Monolith,” Worsley et al., J. Phys. Chem. Letter, 2010, 132(40), 14067-14069, is incorporated herein by reference in its entirety.
The article, “Advanced Carbon Aerogels for Energy Applications,” Biener et al., Energy & Environmental Science, 2011, 4, 656-667, is incorporated herein by reference in its entirety.
US Patent Publication 2010/0144904 describes graphene aerogel but the material is not crosslinked and is not air-dried.
A high-density graphene-based monolith described herein can be a black monolith that is mechanically robust, electrically conductive, and of high density. Monolith is a term known in the art. Monolith and methods for making monolith are disclosed in, for example, U.S. Pat. No. 5,207,814, U.S. Pat. No. 5,885,953, U.S. Pat. No. 5,879,744, U.S. Pat. No. 7,378,188, U.S. Pat. No. 7,410,718, and U.S. Pat. No. 7,811,711.
The high-density graphene-based monolith can comprise a three-dimensional structure of graphene sheets crosslinked by chemical linkage such as covalent carbon-carbon bond. In one embodiment, 50% or more, or 70% or more, or 90% or more of the crosslinking covalent bonds are sp2 bonds.
In one embodiment, the high-density graphene-based monolith is substantially free of graphene sheets interconnected only by physical crosslinks (e.g. Van der Waals forces). In one embodiment, less than 10%, or less than 5% or less than 3%, or less than 1% of the graphene sheets are interconnected only by physical crosslinks.
In one embodiment, the high-density graphene-based monolith is substantially free of graphene sheets interconnected only by metal crosslinks (e.g., noble metal such as Pd). In one embodiment, less than 10%, or less than 5% or less than 3%, or less than 1% of the graphene sheets are interconnected only by metal crosslinks.
In one embodiment, the high-density graphene-based monolith is substantially free of graphene sheets with hydroxide or epoxide functionalities. In another embodiment, 10% or less, or 5% or less, or 3% or less, or 1% or less, or 0.5% or less, or 0.1% or less of the carbon atoms in the graphene-based monolith are connected to a hydroxide or epoxide functionality.
The high-density graphene-based monolith comprises, for example, restacking or substantial restacking of graphene sheets. The graphene sheets can have lateral dimensions of, for example, 10 nm or more, 50 nm or more, or 100 nm or more, including 10 nm to 50 nm. The surfaces of the graphene sheets can be, for example, free or substantially free of nanoparticles.
In one embodiment, the high-density graphene-based monolith is not made by stacking non-organic material, such as metals, between graphene sheets.
The high-density graphene-based monolith can have an atomic oxygen content of, for example, 10% or less, or 5% or less, or 3% or less, or 1% or less. The high-density graphene-based monolith can be mesoporous. The average pore size can be, for example, less than 20 nm.
The high-density graphene-based monolith can have a density of, for example, 0.2 g/cm3 or more, or 0.5 g/cm3 or more, or 1.0 g/cm3 or more, or 1.5 g/cm3 or more.
The high-density graphene-based monolith can have a bulk electrical conductivity of, for example, 100 S/cm or more, or 200 S/cm or more, or 500 S/cm or more, or 1,000 S/cm or more, or 1,500 S/cm or more, or 2,000 S/cm or more.
The high-density graphene-based monolith can have a surface area of, for example, 200 m2/g or more, 100 m2/g or more, or 70 m2/g or more, or 50 m2/g or more, or m2/g or more.
The high-density graphene-based monolith can have a Young's modulus of, for example, 1 GPa or more, or 5 GPa or more, or 10 GPa or more.
The high-density graphene-based monolith can have a failure stress of, for example, 0.2 GPa or more, or 0.5 GPa or more, or 1 GPa or more.
The high-density graphene-based monolith can have a compressive strength of, for example, 50 MPa or more, or 100 MPa or more, or 200 MPa or more.
An alternative embodiment is for a high-density carbon nanotube-based monolith. In particular, a composition is provided comprising at least one high-density carbon nanotube-based monolith, said monolith comprising carbon nanotubes crosslinked by nanoparticles and having a density of at least 0.2 g/cm3.
In some embodiments, the carbon nanotubes are single-walled carbon nanotubes or double-walled carbon nanotubes. More generally, the carbon nanotubes can be multi-walled nanotubes.
In one embodiment, the carbon-nanotube-based monolith comprises at least 20 wt. % of carbon nanotubes. In one embodiment, the carbon-nanotube-based monolith comprises at least 40 wt. % of carbon nanotubes. In one embodiment, the carbon-nanotube-based monolith comprises at least 60 wt. % of carbon nanotubes. In one embodiment, the carbon-nanotube-based monolith comprises at least 80 wt. % of carbon nanotubes.
In one embodiment, the monolith has a density of at least 0.2 g/cm3. In one embodiment, the monolith has a density of at least 0.5 g/cm3. In one embodiment, the monolith has a density of at least 0.7 g/cm3.
In one embodiment, the monolith has an electrical conductivity of at least 200 S/cm or more. In one embodiment, the monolith has an electrical conductivity of at least 400 S/cm or more.
In one embodiment, the monolith has a Young's modulus of at least 0.5 GPa. In one embodiment, the monolith has a Young's modulus of at least 1 GPa.
Precursors to graphene are known in the art. For example, graphene oxide is a general term for oxidized graphene, which can be a precursor to graphene. Closely related precursors can include, for example, graphite oxide, single layer graphene oxide, exfoliated graphite, and the like. See US 2012/0034442, incorporated by reference in its entirety.
Carbon nanotubes are known in the art. See US 2010/0187484, incorporated by reference in its entirety. For example, the carbon nanotube can be a single-walled carbon nanotube, a double-walled carbon nanotube, or a multi-walled carbon nanotube.
In some embodiments, the reaction mixture comprises a graphene oxide (GO) suspension. Methods for making GO are known in the art and disclosed in, for example, Hummer, J. Am. Chem. Soc., 80:1339 (1958), which is incorporated herein by reference in its entirety. In one embodiment, the GO suspension is an aqueous suspension. In another embodiment, the GO suspension is a suspension of at least one organic solvent, such as alcohol, dimethylformamide, tetrahydrofuran, ethylene glycol, N-methylpyrrolidone, etc. In one embodiment, the GO suspension is an aqueous suspension made by sonicating GO in deionized water. The time for sonication can range from 0.25-24 hours. The concentration of GO in the reaction mixture can be 0.1 mg/cm3 or more, or 1 mg/cm3 or more, or 2 mg/cm3 or more, or 5 mg/cm3 or more, or 10 mg/cm3 or more.
In some embodiments, the reaction mixture comprises a carbon nanotube suspension. See Worsley, et al., J. Mater. Chem., 19:3370 (2009), which is incorporated herein by reference in its entirety. In one embodiment, the carbon nanotube suspension is an aqueous suspension. In another embodiment, the carbon nanotube suspension is a suspension of at least one organic solvent. In one embodiment, the carbon nanotube suspension is an aqueous suspension made by sonicating carbon nanotubes in deionized water. The time for sonication can range from 0.25-24 hours. The concentration of carbon nanotubes in the reaction mixture can be, for example, 0.1 to 80 wt. %, 0.1 to 60 wt. %, 0.1 to 50 wt. %, or 0.1-32 wt. %. The upper percentage for the carbon nanotube concentration is not particularly limited except by practicalities for a particular system.
The reaction mixture may also comprise additional reactant known for sol gel reactions, though it is may not be necessary for gelation. In one embodiment, the reaction mixture comprises resorcinol-formaldehyde (RF), phloroglucinol-formaldehyde, phenol-formaldehyde, cresol-formaldehyde, or phenol-furfuryl alcohol. In one embodiment, the reaction mixture is free of RF. In another embodiment, the reaction mixture comprises RF. In a particular embodiment, the GO-to-RF ratio is 0.1 or more.
The reaction mixture also can comprise at least one sol gel catalyst. In one embodiment, the catalyst is an acid catalyst. In another embodiment, the catalyst is a base catalyst. An example is a hydroxide catalyst. Suitable catalysts include, but are not limited to, nitric acid, acetic acid, ascorbic acid, hydrochloric acid, sulfuric acid, sodium carbonate, sodium hydroxide, ammonium hydroxide, and calcium sulfate. The reactant-to-catalyst ratio may range from 10 to greater than 1000.
High-density graphene-based monoliths and high-density carbon-nanotube-based monoliths can be made from the reaction mixture according to the following steps: (i) curing the reaction mixture to produce a wet gel; (ii) drying the wet gel to produce a dry gel, said step is substantially free of supercritical drying and freeze drying; and (iii) pyrolyzing the dry gel to produce a high-density graphene-based monolith or a high-density carbon-nanotube-based monolith.
In one embodiment, the reaction mixture is cured at a temperature of 25-100° C. to produce a wet gel. In another embodiment, the reaction mixture is cured for 12-72 hours at a temperature of 85° C. In a further embodiment, the reaction mixture is cured at atmospheric pressure.
In one embodiment, the wet gel is subjected to solvent exchange to remove reaction by-products. Suitable solvent include, but are not limited to, DI water. In another embodiment, the wet gel is subjected to solvent exchange to remove water. Suitable solvents include, but are not limited to, acetone.
In one embodiment, the wet gel is dried under ambient temperature and pressure. In one embodiment, the wet gel is dried under ambient temperature and pressure for at least 24 hours. The application of heat can be avoided. In particular, the drying step can comprise drying the wet gel to produce a dry gel without application of heat to raise the temperature beyond ambient temperature. The drying step is carried out without supercritical drying. If desired, some heat can be applied for increasing the speed of drying, but it is not essential or required in many or all embodiments.
In one embodiment, the dry gel is pyrolyzed in an inert gas to produce a high-density graphene-based monolith or a high-density carbon-nanotube-based monolith. Suitable inert gases include, but are not limited to, nitrogen. The pyrolyzing temperature can be 500° C. or more, or 800° C. or more, or 1000° C. or more. The pyrolyzing temperature can be, for example, less than 2,500° C., or less than 2,000° C., or less than 1,500° C.
The monoliths, including high-density graphene-based monolith and the high-density carbon-nanotube-based monolith, described herein can be used in a variety of devices. For example, they can be used in electrodes, batteries, capacitors, supercapacitors, sensors, actuators, membranes, structural elements, furnace components, catalyst supports, and hydrogen storage devices. In a particular embodiment, the high-density graphene-based monolith described herein is used in a lithium battery electrode. Other applications can include, for example, lightweight armor, missile nose cone, and high temperature/thermal shock applications.
In addition, graphene monoliths can also be used to shield sensitive electronic devices like cell phones, personal digital assistants, computers, and hospital equipment from Electromagnetic Interference (EMI) and Radio Frequency Interference (RFI). Shielding must be electrically conductive and traditionally made of metal, which poses a weight problem for smaller electronics. Additionally, graphene monoliths are lightweight materials that outperform metal shielding. Positive attributes of graphene monoliths in this application include light weight, resistance to corrosion, and flexibility.
Additional embodiments are provided in the following non-limiting working examples.
In a typical reaction, graphene oxide (GO) was suspended in deionized water and thoroughly dispersed using a VWR Scientific Model 75T Aquasonic (sonic power ˜90 W, frequency ˜40 kHz). The concentration of GO in the reaction mixture was 2 wt %. To determine the optimal conditions for GO dispersion, a range of sonication times (4 to 24 hrs) was evaluated. Once the GO (3 ml) was dispersed, concentrated ammonium hydroxide (633 μl) was added to the dispersion. The sol-gel mixture was then transferred to glass molds, sealed and cured in an oven at 85° C. for 12-72 h. The resulting gels were then removed from the molds and washed with deionized water to remove reaction byproducts and excess ammonium hydroxide. Then the gels were washed in acetone to remove all the water from the pores of the gel network. The wet gels were subsequently dried under ambient conditions to yield the high-density reduced GO assemblies. Some samples were also dried using supercritical CO2 to produce low-density reduced GO assemblies for comparison. The reduced GO assemblies were thermally reduced via pyrolysis at 1050° C. under a N2 atmosphere for 3 h. The 3D graphene macroassemblies were isolated as black cylindrical monoliths.
Field-emission scanning electron microscopy (SEM) characterization was performed on a JEOL 7401-F at 5-10 keV (20 mA) in secondary electron imaging mode with a working distance of 2-8 mm. Surface area determination were performed by Brunauer-Emmett Teller (BET) and Barrett-Joyner-Halenda (BJH) methods using an ASAP 2000 Surface Area Analyzer (Micromeritics Instrument Corporation) (Gregg et al. Adsorption, Surface Area and Porosity, 2nd ed.; Academic: London, 1982). Samples of approximately 0.1 g were heated to 150° C. under vacuum (10−5 Torr) for at least 24 hours to remove all adsorbed species. X-ray diffraction (XRD) measurements were performed on a Bruker AXS D8 ADVANCE X-ray diffractometer equipped with a LynxEye 1-dimensional linear Si strip detector. The samples were scanned from 5 to 75° 2θ. The step scan parameters were 0.02° steps and 2 s counting time per step with a 0.499° divergence slit and a 0.499° antiscatter slit. The X-ray source was Ni-filtered Cu radiation from a sealed tube operated at 40 kV and 40 mA. Phases in the samples were identified by comparison of observed peaks to those in the International Centre for Diffraction Data (ICDD PDF2009) powder diffraction database, and also peaks listed in reference articles. Goniometer alignment was ensured using a Bruker-supplied Al2O3 standard.
Monoliths were machined with a 6-mm-diameter cylindrical endmill rotating at a speed of 2×104 revolutions per minute, yielding macroscopically flat surfaces needed for mechanical characterization by indentation. The samples were indented in the load-controlled mode in an MTS XP nanoindenter with a flat punch diamond tip with an effective diameter of 62 microns. Representative indentation stress (σ) and strain (ε) were defined as σ=4P/(πD2) (i.e., the average contact pressure) and ε=4h/(πD)≈h/D (i.e., the proportionality coefficient between σ and the reduced modulus in the elastic regime) (Kucheyev et al., Acta Materialia 57, 3472, 2009). Here, P is the load, D is the indenter tip diameter, and h is the indenter displacement. Both loading and unloading rates were kept constant to maintain an indentation strain rate of 10−3 s−1 (Kucheyev et al., Acta Materialia 57, 3472, 2009). Elastic properties are characterized by the Young's modulus, which was calculated based on the initial slope of the unloading curve according to the Oliver-Pharr method (Oliver et al., Journal of Materials Research 7, 1564, 1992) for maximum loads below those resulting in failure events. In Oliver-Pharr calculations, we assumed Poisson's ratios of diamond and aerogels of 0.07 and 0.2, respectively, and the Young's modulus of diamond of 1141 GPa (Kucheyev et al., Acta Materialia 57, 3472, 2009). Several (>10) measurements of the Young's modulus, failure stress, and failure strain were made on different sample locations, and results were averaged. The error bars given are standard deviations. Electrical conductivity was measured using the four-probe method with metal electrodes attached to the ends of cylindrical samples. The amount of current transmitted through the sample during measurement was 100 mA, and the voltage drop along the sample was measured over distances of 3 to 6 mm. Seven or more measurements were taken on each sample, and results were averaged. Bulk densities of the samples were determined from the physical dimensions and mass of each sample.
Described here is a straightforward relatively low-temperature method to realize macroscopic 3D graphene-derived carbons (GDCs) with isotropic properties approaching those of graphene sheets. Important factors for assembling a macrostructure with such properties are (i) the development of strong covalent links between graphene sheets that facilitate both electrical conductivity and structural reinforcement, (ii) sufficient restacking of graphene sheets to reach relatively high densities of ˜1 g/cm3, and (iii) an assembly that can be carbonized at relatively low temperatures (˜1000° C.).
In order to form strong links between graphene sheets in GDCs, a method based on chemical cross-linking of individual sheets of graphene oxide (GO) suspended in water was used. Such cross-linking involves various GO functional groups (e.g., epoxide and hydroxide), yielding a reduced GO gel. Similar approach was used in the synthesis of exceptionally stiff and electrically conductive low-density graphene macroassemblies (GMAs) (Worsley et al., Chem Commun, 48, 8428 (2012)). The restacking of graphene sheets in the GDC was achieved by simply drying the reduced GO gel under ambient conditions instead of using a supercritical solvent extraction method that preserves the low-density structure and minimizes sheet restacking in GMAs. The dried monoliths were then annealed at about 1000° C. to reduce the organic cross-links to sp2 carbon cross-links. Resultant GDCs displayed isotropic bulk properties such as electrical conductivities and Young's moduli that are 3-6 orders of magnitude higher than for any previously reported 3D graphene assembly, and exceeding isotropic graphite that is nearly twice as dense.
Synthesis of GDCs was carried out via gelation of a GO suspension under basic conditions. Full experimental details is provided above in the Material Synthesis section. Briefly, in a typical synthesis, ultrasonication is used to disperse 2 wt % GO in deionized water. Concentrated NH4OH was added (211 μl/g GO suspension) to the suspension, which was then sealed and placed in an oven at 85° C. to gel. After gelation, the reduced GO gel was washed first in deionized water and then in acetone. After that, the gel was allowed to dry under ambient conditions for at least 24 hours, followed by annealing at 1050° C. under nitrogen to yield the final GDC with a monolith density of ˜1.0 g/cm3. This is an ˜10-fold increase in the density compared to GMAs that have densities of ˜0.10 g/cm3. Importantly, the randomly orientated self-assembly during gelation combined with the capillary force-induced shrinkage led to the formation of a completely isotropic material.
The difference between the microstructure of GDCs and GMAs was illustrated by scanning electron microscopy (SEM) images in
In contrast, no fine sheet-like features were distinguishable in the GDC in
The x-ray diffraction (XRD) patterns for GDCs and GMAs also showed significant deviations (
Despite having a density of close to half of that of perfectly stacked graphene sheets (2.2 g/cm3) or even commercial grade graphite (1.6-1.9 g/cm3), the mechanical properties of the GDC exceeded those of graphite. Nanoindentation results (
Considering that Young's modulus depends superlinearly on monolith density, ρ, for nanoporous materials with an exponent, n, in the range of 2-4,
The bulk electrical conductivity of the GDC, determined via the four-probe method, was 1,750 S/cm, which is likely larger than for any 3D graphene assembly reported.
In a typical reaction, purified CNTs were suspended in deionized water and thoroughly dispersed using a VWR Scientific Model 75T Aquasonic sonication bath (sonic power ˜90 W, frequency ˜40 kHz). The concentration of CNTs in the reaction mixture ranged from 0 wt % to 2 wt %. To determine the optimal conditions for CNT dispersion, a range of sonication times (4 to 24 hrs) were evaluated. Once the CNTs were dispersed, resorcinol (1.235 g, 11.2 mmol), formaldehyde (1.791 g, 22.1 mmol), and sodium carbonate catalyst (5.95 mg, 0.056 mmol) were added to the reaction solution. The resorcinol to catalyst ratios (R/C) employed for the synthesis of the composites range from 50 to 200. The sol-gel mixture was then transferred to glass molds, sealed and cured in an oven at 85° C. for 72 h. The resulting gels were then removed from the molds and washed with acetone for 72 h to remove water from the pores of the gel network. The wet gels were subsequently dried under ambient conditions and pyrolyzed at 1050° C. under a N2 atmosphere for 3 h. The composite materials were isolated as black cylindrical monoliths. Foams with CNT loadings ranging from 0 to ˜90 wt %, or ranging from 0 to ˜99 wt %, were prepared by this method. The rest of the material can be, in many cases, carbon aerogel particles that “glue” the CNTs together. These particles can, it is believed, come from the resorcinol-formaldehyde (RF) solution in which the CNTs are originally suspended and gelled. The RF forms an organic gel which connects the CNTs. The organic “glue” is converted to carbon during pyrolysis at, for example, 1050° C. in nitrogen.
Hence, described herein in some embodiments is a straightforward method to realize high-density graphene-based macroassemblies with isotropic mechanical and electronic transport properties approaching those of individual graphene sheets. The design strategy involved, in some embodiments, direct cross-linking of graphene sheets via the functional groups in graphene oxide and sufficient restacking of the graphene sheets to increase the material density. The nature of the synthesis led to a much lower temperature used than for the synthesis of commercial isotropic graphite and facilitated fabrication with few limits on the size or shape. The development of 3D bulk macrostructures retaining properties of individual graphene sheets will both expand and accelerate the commercialization of graphene-based technologies and products.
Finally, the following references can be referred to practicing embodiments described herein and some are noted in
This application claims priority to U.S. provisional application Ser. No. 61/745,528 filed Dec. 21, 2012, which is hereby incorporated by reference for all purposes.
The United States Government has rights in the invention pursuant to Contract No. DE-AC52-07NA27344 between the U.S. Department of Energy and Lawrence Livermore National Security, LLC, for the operation of Lawrence Livermore National Laboratory.
| Number | Date | Country | |
|---|---|---|---|
| 61745528 | Dec 2012 | US |
