Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom

Abstract

Compositions and methods of producing discrete nanotubes and nanoplates and a method for their production. The discrete nanotube/nanoplate compositions are useful in fabricated articles to provide superior mechanical and electrical performance. They are also useful as catalysts and catalyst supports for chemical reactions.

Claims

1. A composition comprising: inorganic plates with individual plate thickness of less than 10 nanometers wherein the plates are graphene nanoplates; and discrete multiwall carbon nanotubes having a diameter ranging from about 1 nanometer to 150 nanometers, an oxidation level of from about 1 weight % to about 15 weight %, and wherein the carbon nanotubes have an aspect ratio ranging from about 10 to 500.

2. The composition of claim 1, wherein the inorganic plates and discrete tubes are present at a weight ratio of about 1:100 to 100:1.

3. The composition of claim 1, wherein the inorganic plates are interspersed with the discrete multiwall carbon nanotubes.

4. The composition of claim 1 wherein the inorganic plates are oxidized.

5. The composition of claim 1, further comprising inorganic materials selected from the group consisting of: ceramics, clays, silicates, metal complexes and salts.

6. The composition of claim 1 further comprising at least one electroactive material.

7. The composition of claim 1 further comprising at least one transition metal complex or active catalyst species.

8. The composition of claim 7, wherein the inorganic plates and discrete tubes are present at a weight ratio of about 1:100 to 100:1.

9. The composition of claim 1, wherein the carbon nanotubes have an aspect ratio ranging from about 25 to 500.

10. The composition of claim 1, wherein the composition is incorporated into a tire, industrial rubber part or wind blade.

11. The composition of claim 1, wherein the composition is incorporated into a battery.

12. The composition of claim 1, wherein the composition is incorporated into a capacitor.

13. The composition of claim 1, wherein the composition is incorporated into a solar cell.

14. The composition of claim 1, wherein the composition is incorporated into a powder or liquid mixture.

15. The composition of claim 1, wherein the composition is incorporated into a catalyst or catalyst support.

16. The composition of claim 1, wherein the composition is incorporated into a concrete mixture.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) For a more complete understanding of the present disclosure, and the advantages thereof, reference is now made to the following descriptions to be taken in conjunction with the accompanying figures for describing specific embodiments of the disclosure, wherein:

(2) FIG. 1 shows a secondary electron micrograph of graphene plates with a discrete carbon nanotube of this invention. The magnification is 200,000?.

(3) FIG. 2 shows a secondary electron micrograph of lithium iron phosphate and magnesium hydroxide plates with a discrete carbon nanotube of this invention. The magnification is 5,060?.

(4) FIG. 3 shows a secondary electron micrograph of zirconium phosphate plates with discrete carbon nanotube of this invention. The magnification is 155,000?.

DETAILED DESCRIPTION

(5) In the following description, certain details are set forth such as specific quantities, sizes, etc., so as to provide a thorough understanding of the present embodiments disclosed herein. However, it will be evident to those of ordinary skill in the art that the present disclosure may be practiced without such specific details. In many cases, details concerning such considerations and the like have been omitted inasmuch as such details are not necessary to obtain a complete understanding of the present disclosure and are within the skills of persons of ordinary skill in the relevant art.

(6) While most of the terms used herein will be recognizable to those of ordinary skill in the art, it should be understood, however, that when not explicitly defined, terms should be interpreted as adopting a meaning presently accepted by those of ordinary skill in the art. In cases where the construction of a term would render it meaningless or essentially meaningless, the definition should be taken from Webster's Dictionary, 3rd Edition, 2009. Definitions and/or interpretations should not be incorporated from other patent applications, patents, or publications, related or not, unless specifically stated in this specification or if the incorporation is necessary for maintaining validity.

(7) Nanotubes are tubular structures that have a diameter of at least 1 nanometer and up to 100 nanometers. Examples of nanotubes are single, double and multiwall carbon nanotubes or titanium dioxide nanotubes. The aspect ratio is defined as the ratio of the tube length to the tube diameter. Nanoplates are defined as being discernible plates of thickness less than ten nanometers.

(8) Discrete oxidized carbon nanotubes, alternatively termed exfoliated carbon nanotubes, can be obtained from as-made bundled carbon nanotubes by methods such as oxidation using a combination of concentrated sulfuric and nitric acids. The bundled carbon nanotubes can be made from any known means such as, for example, chemical vapor deposition, laser ablation, and high pressure carbon monoxide synthesis. The bundled carbon nanotubes can be present in a variety of forms including, for example, soot, powder, fibers, and bucky paper. Furthermore, the bundled carbon nanotubes may be of any length, diameter, or chirality. Carbon nanotubes may be metallic, semi-metallic, semi-conducting, or non-metallic based on their chirality and number of walls. The discrete oxidized carbon nanotubes may include, for example, single-wall, double-wall carbon nanotubes, or multi-wall carbon nanotubes and combinations thereof.

(9) Graphene is an allotrope of carbon, whose structure is one-atom-thick planar sheets of sp.sup.2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The crystalline or flake form of graphite consists of many graphene sheets stacked together. Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm. Graphene is the basic structural element of some carbon allotropes including graphite, charcoal, carbon nanotubes and fullerenes. It can also be considered as an indefinitely large aromatic molecule, the limiting case of the family of flat polycyclic aromatic hydrocarbons. One method for graphene obtainment consists of mixing low concentrations of graphite in a solvent such as N-methylpyrrolidone then sonicating. Non-exfoliated graphite is eventually separated from graphene by centrifugation.

(10) In one embodiment the inorganic plates are interspersed with the discrete multiwall carbon nanotubes and both the inorganic plates, e.g., graphene, and the discrete multiwall carbon nanotubes are oxidized. In this manner a negative surface charge may cause individual carbon nanotubes to repel each other and potentially prevent or further limit agglomeration and/or entanglement. This along with employing discrete nanotubes may be beneficial in controlling the interplate distance since this distance may be primarily determined by nanotube diameter as opposed to agglomerated nanotubes as used in the prior art. The controlled distance may be useful in applications wherein controlled transport of molecules or ions between the plates is desired.

(11) In another embodiment the composition comprises graphene inorganic plates having an individual plate thickness of less than 10 nanometers and discrete multiwall carbon nanotubes having a diameter ranging from about 1 nanometer to 150 nanometers, an oxidation level of from about 1 weight % to about 15 weight %, and an aspect ratio ranging from about 10 to 500. Depending upon the desired ion transport it may be beneficial if the composition does not include polymer particles in amounts such that the ion transport is materially affected in an undesired manner.

(12) One of ordinary skill in the art will recognize that many of the specific aspects of this invention illustrated utilizing a particular type of nanotube or nanoplate may be practiced equivalently within the spirit and scope of the disclosure utilizing other types of nanotubes and nanoplates.

EXAMPLE 1

(13) Evaluation of Discrete Carbon Nanotubes and Graphene Dispersion Characteristics in Surfactant-Stabilized Aqueous Suspensions

(14) Graphene (Rice University) and multiwall carbon nanotubes (C-9000, C-Nano) of diameter about 13 nm and are combined in the weight ratio of 1:3, respectively. A 1% w/v dispersion of the mixture is prepared in a 3:1 sulfuric (96%, KMG)/nitric (70%, Honeywell) acid solution and sonicated using a sonicator bathe while maintaining a bath temperature in the 30? C.-35? C. range for 3 hours. Following sonication, each formulation was B?chner-filtered on a 5 ?m PVDF membrane (Whatman) with a 200 mL portion of water. The samples were dried for two hours at 80? C. in a vacuum oven. An electron micrograph will show carbon nanotubes separating graphene plates, for example shown in FIG. 1.

(15) 0.05 g of the dried graphene carbon nanotube mixture and 0.15 g of sodium dodecyl sulfate (Sigma-Aldridge) was added to a 20 mL graduated flask and filled o the 20 mL mark with water. The flask was sonicated in a bath for a period of 1 hour, the temperature monitored in the same fashion described above. After sonication, a 1 mL sample was diluted with water to final total carbon concentration of 2.5?10.sup.?5 g/mL and evaluated by UV-vis spectrophotometry (BioSpec-1601, Shimadzu). Following the measurement of the first absorbance spectrum, the same specimen was analyzed at 5, 15, 30, 45 and 60-minute time periods at a wavelength of 500 nm to evaluate the stability of the mixture in water. The decay in initial absorbance value at 500 nm after 60 minutes was determined as 0.4%.

(16) Comparison 1

(17) Comparison 1 repeats the experimental procedure as example 1 but with graphene only. The decay in initial absorbance value at 500 nm after 60 minutes was determined as 12.1%.

(18) Comparison 2

(19) Comparison 2 repeats the experimental procedure as example 1 but with multiwall carbon nanotubes only. The decay in initial absorbance value at 500 nm after 60 minutes was determined as 0%.

(20) The discrete carbon nanotubes of example 1 are shown by the UV spectroscopy to have provided stability to the graphene dispersions by interspersing between the graphene plates.

EXAMPLE 2

(21) 0.039 grams of multiwall carbon nanotubes with an oxidation level of 8 weight percent is added to 0.0401 grams of lithium iron phosphate and 40 grams of deionized water in a glass bottle. The mixture is sonicated for 13 minutes using a sonicator bath at 25 degrees centigrade, after which no carbon nanotube particles are observed by visual inspection. 1 ml of the sonicated mixture is then mixed with 0.14 mls of a 0.1% weight/volume mixture of magnesium hydroxide in deionized water and then diluted with more deionized water so that the volume was 4 ml. This final mixture was sonicated a further 15 minutes at 25 degrees centigrade. For examination by electron microscopy a drop of this solution is then placed on a carbon tape and dried. The result is seen in FIG. 2 showing discrete carbon nanotubes on the surface and between plates.

EXAMPLE 3

(22) Discrete Multiwall Carbon Nanotubes with Zirconium Phosphate Nanoplates, Zr(HP0.sub.4)2H.sub.20

(23) A dispersed solution of carbon nanotubes was prepared from 10 mg of multi-wall carbon nanotubes placed in 2 mL of a mixture of Zr(HP0.sub.4)2.H.sub.20 and tetrabutylammonium hydroxide (5 weight % Zr(HP0.sub.4.H.sub.20; 1:0.8 ratio of Zr(HP0.sub.4)2H.sub.20:tetrabutylammonium hydroxide). The solution was subsequently diluted to 30 mL and then sonicated for 2 hours. The solution is stable for at least 24 hours. A drop of this solution is placed on a carbon tape and dried. The secondary electron microscope picture, FIG. 3, reveals zirconium phosphate nanoplates of approximate plate diameter of 200 nanometers interspersed with discrete carbon nanotubes.