METHOD FOR COST-EFFICIENT INDUSTRIAL PRODUCTION OF GRAPHITE OXIDE, GRAPHENE OXIDE AND GRAPHENE

Abstract

A method of chemical oxidation and exfoliation of graphite ore using inorganic oxidizing potassium-type agents in an acid medium is disclosed. The product of the claimed method, according to electron microscopy analysis, is sheets or nanoscale graphene oxide plates with thicknesses less than 100 nm.

Claims

1. An industrial method of producing large-scale quantities of graphite oxide, graphene oxide and/or graphene, the method comprising the steps of: a. ultrafine grinding of graphite ore; b. flotation purification of graphite ore in bi-distilled water; at a temperature of 90 C. or lower, c. graphite oxidative transformation of b) to graphite oxide; d. separation and/or purification of the graphite oxide obtained in the oxidation of graphite in c); e. obtaining graphene oxide from graphite oxide obtained in d); and f. obtaining graphene from graphene oxide of e) at a temperature less than 200C.

2. The method of claim 1, further comprising the step of separating sheet graphite ore at a temperature below 200 C.

3. The method according to claim 1, wherein ultrafine grinding comprises grinding the graphite ore to a fineness of less than 150 microns.

4. The method of claim 2, wherein the sheet separation is conducted by exfoliation or intercalation.

5. The method of claim 4, wherein the sheet separation is carried out with chemical treatments.

6. The method of claim 4, wherein the sheet separation further comprises the use of ultrasound.

7. The method of claim 1, wherein step f) is performed at a temperature less than 100 C.

8. The method of claim 1, wherein step c) is performed by a technique belonging to the following group: treatment or chemical reduction, intercalation, exfoliation and reduction with hydroiodic acid.

9. The method of claim 8, wherein step c) is carried out by chemical treatment of the graphite ore using potassium permanganate, sulfuric acid, hydrogen peroxide and distilled water.

10. The method of claim 9, wherein step c) is carried out by chemical treatment of graphite ore using: weight ratios of graphite ore/potassium permanganate among to ; and a reaction volume consisting of: 79.625 vol % of sulfuric acid to 98%, 19.625 vol % of phosphoric acid at 85%, and 0.75 vol % hydrogen peroxide at 30%; or 87.125 vol % of sulfuric acid to 98%, 12.125 vol % of phosphoric acid at 85%, and 0.75 vol % hydrogen peroxide at 30%; or 89.625 vol % of sulfuric acid to 98%, 9.625 vol % of phosphoric acid at 85%, and 0.75 vol % hydrogen peroxide at 30%.

11. The method of claim 1, wherein step d) is performed by a technique belonging to the following group: centrifugation and decantation of the supernatant.

12. The method of claim 1, further comprising the step of separating sheet graphite ore at a temperature below 100 C.

13. The method of claim 1, wherein step e) is performed by separating the sheets of graphene oxide.

14. The method of claim 13, wherein the separation of the sheets of graphene oxide is performed using a technique belonging to the following group: intercalation and exfoliation.

15. The method of claim 14, wherein the separation of the sheets is performed by ultrasonic exfoliation.

16. The method of claim 1, wherein ultrafine grinding comprises grinding the graphite ore to a fineness of less than 100-150 microns.

17. The method of claim 1, wherein step f) is performed by a technique of reducing the graphene oxide to the following group: chemical reduction with hydroiodic acid, electrochemical and combinations thereof.

18. A product obtained by the method of claim 1, wherein the product is graphite oxide, graphene oxide or graphene.

19. (canceled)

20. A method of using the product of claim 18 for applications in catalysis.

21. A method of using the product of claim 18 for applications in microelectronics.

22. A method of using the product of claim 18 for applications in energy storage.

Description

BRIEF DESCRIPTION OF THE DRAWING(S)

[0018] FIG. 1 is a flow-diagram of the claimed invention illustrating the sequential order of the claimed method steps.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The method of the present invention, which is particularly suited to scaling and industrial use, employs a novel variant of the well-known Hummers Method, which yields graphite oxide that, with subsequent exfoliation, produces graphene oxide. In the method described in the present invention, other products such as graphene oxide and reduced oxide graphene (graphene), valuable materials themselves, can also be obtained by applying conventional methods. The present invention therefore provides an advantageous method of producingat industrial scalegraphite oxide, graphene oxide and/or graphene, as raw graphitic materials (mineral graphite, etc.) are easily available in Sonora State in Mexico, and there is abundant mineral graphite worldwide and its exploitation is much cheaper than synthetic graphite or other high priced graphitic derivative materials.

[0020] The use of graphite ore has many current economic, environmental, energy and strategic advantages as it is a product that is naturally occurring in abundance approximately 100 km from the city of Hermosillo Sonora in Mexico, where it is marketed for many standard applications in industry, thereby ensuring a ready supply. The economic interest of implementing the method of the present invention is thus very high.

[0021] Therefore, an aspect of the present invention relates to an industrial process, hereinafter referred to as the claimed process, for obtaining graphite oxide from readily available graphitic materials (graphite ore). Subsequent sheet separation can be accomplished by exfoliation or intercalation thermal shock, among other techniques known to anyone skilled in the matter. Preferably the sheet separation is carried out by exfoliation using ultrasound (sonication).

[0022] In application, the claimed process, besides the direct production of graphite oxide by oxidative transformation of graphite ore, can be used to obtain other products such as graphene oxide and/or graphene, by adding intermediate reaction steps. Therefore, in another particular embodiment, the method further comprises the following process steps: [0023] a) a process of ultra-fine grinding of ore graphite to less than 150 microns (m) in size, preferably 100-150 microns (m), [0024] b) flotation purification of ore graphite in bi-distilled water at a temperature of 90 C., [0025] c) graphite oxidative transformation of b) to graphite oxide, [0026] d) separation and/or purification of the graphite oxide obtained in the oxidation of graphite in c), [0027] e) obtaining graphene oxide from graphite oxide obtained in d), and [0028] f) obtaining graphene from graphene oxide of e); [0029] where the temperature at any stage is less than 200 C., preferably below 100 C. In a preferred embodiment, all steps are performed sequentially.

[0030] In one embodiment of the claimed method, the graphitic material a) is graphite ore material obtained easily and with greater availability than other conventional graphitic materials known in the manufacture of graphene.

[0031] In the claimed invention, the graphitic material may also be used without controlling the particle size; however, if particle size is not controlled for, longer reaction times may be required, and/or the use of additional oxidizing agents such as those indicated above. Thus, in another embodiment of the claimed invention, step a) is omitted, and the method commences at step b) or c).

[0032] A particular embodiment of the invention is the method of the invention wherein step c) transformation of graphite in a) or b) in graphite oxide by chemical treatment of graphite is conducted using as reagents potassium permanganate, sulfuric acid, phosphoric, hydrogen peroxide and bi-distilled water, although the method is not limited to those reagents.

[0033] In a further preferred embodiment, the method of the present invention step c) of transforming graphite in a) or b) in graphite oxide is conducted by a chemical treatment using weight ratios of graphite/potassium permanganate from to depending on the quality of graphite. Preferred reaction volumes corresponding to 87.5 vol % sulfuric acid and 12.5 vol % phosphoric acid, adding at the end of 0.75% hydrogen peroxide, the percentages being expressed by volume relative to the total reaction volume, these being variable preferable ratios depending on the material characteristics.

[0034] Another particular object of the invention is the method of the invention in which step d) purification of the graphite oxide obtained in the oxidation of graphite in c) is carried out by, for illustrative purposes and without limiting the scope of the invention, a technique belonging to the following group: decanting the supernatant and centrifugation. In a further preferred embodiment, this purification takes place by repeating in sequence the aforementioned separation of oxides, after adding distilled water, until the decanted water has a pH measurement between 3 and 4. However, another type of water may also be used to wash the obtained graphite oxide, along with any other conventional method such as, for example, filtration, dialysis or addition of other solvents.

[0035] Thus, a particular object of the invention is the method of the invention in which step e) of obtaining graphene oxide from graphite oxide obtained in d) is carried out by separating the sheets of graphene oxide.

[0036] A particular embodiment of the invention is the method of the invention in which the separation of the sheets of graphene oxide of step e) is performed by a technique, for illustrative purposes and without limiting the scope of the invention, to the following group: exfoliation and thermal shock. Moreover, in this direction the method described in this patent application may comprise the delamination of graphene oxide, accompanied by a reduction of oxygen functional groups, for example by heat treatment without exfoliates oxide material. See US2009/0028777A1.

[0037] In a further preferred embodiment, the separation of the sheets of graphene oxide of step e) of the method of the invention is carried out by exfoliating oxides prepared from ore graphite by ultrasonic treatment. This should be done in periods between 60 minutes to six hours in order to produce graphene oxide.

[0038] Another particular object of the invention is the method of the invention in which step f) to obtain graphene from graphene oxide e) is performed by, for illustrative purposes and without limiting the scope of the invention, a technique of reducing using one or more reducing agents selected from among the following group: as chemical reduction with hydrogen, electrochemical and combinations thereof. See also WO2011/016889A2 (examples of reductions in oxides of graphite and graphene oxides).

[0039] Another object of the invention is the product obtained by the method of the invention, hereinafter product of the invention, wherein the product belongs to the following group: graphite oxide, graphene oxide and graphene.

[0040] Finally, another object of the invention is the use of the product of the invention for applications such as, for illustrative purposes and without limiting the scope of the invention, those belonging to the following group: catalysts, microelectronics and energy storage. See also Han D. L., Yan L. F., Chen W. F., Li W., Preparation of chitosan/graphene oxide composite film with enhanced mechanical strength in the wet state. CARBOHYD. POLYM., 2011, 83, 653-658 and Gonzlez Z., Botas C, Alvarez P., Roldn S., Blanco C, Santamara R., Granda M., Menendez R. Thermally reduced graphite oxide as possitive electrode in vanadium redox flow batteries. CARBN, 2012, 50 (3), 828-834.

EXAMPLES

[0041] The following describes a series of tests performed by the inventor, which are representative of the effectiveness and scalability of the method of the invention for using graphite ore to preparing graphite oxide, graphene oxide and graphene.

Example 1

Using 4 g of Graphite Ore to Produce its Oxide and Graphene Oxide by Chemical Means

[0042] Obtaining graphite oxide from ore graphite was performed as follows. In a beaker of 500 ml are added 50 ml of phosphoric acid to 85% and 350 ml of sulfuric acid at 98% at room temperature, a magnetic bar is added and placed in a grill with stirring for 10 minutes. Subsequently, 4 g of ore graphite, having been ground to a fineness of less than 150 microns, is added and continuously stirred for 10 minutes and then added slowly 24 grams of potassium permanganate, the temperature is raised to 65 C. and left stirring for 8 hours. After the reaction mixture is transferred to a beaker of 1 liter containing 400 ml of bi-distilled water previously frozen and subsequently 3 ml of hydrogen peroxide to 30% are added again and allowed to stir at room temperature for 30 minutes. Let stand for 20 hours. The supernatant was stored and decanted material is transferred to centrifuge tubes and centrifuged at 4500 rpm for 15 minutes. The solid obtained is transferred to a beaker and bi-distilled water is added and stirring is maintained for one hour and allowed to stand for 20 hours, and the rest and above procedure is repeated centrifugation until the pH of the decanted solution around 3 to 4 solution (measured with digital pH meter). The solid thus obtained is graphite oxide from ore graphite.

[0043] To obtain graphene oxide, the graphite oxide was subjected to an ultrasonic treatment at room temperature for 270 minutes. That time is required for delamination and formation of the corresponding graphene oxide.

[0044] Example 2

Using 20 g of Graphite Ore to Produce its Oxide and Graphene Oxide by Chemical Means

[0045] Obtaining graphite oxide from ore graphite was performed as follows. In a beaker of 4 liters were added 250 ml of phosphoric acid to 85% and 1750 ml of sulfuric acid at 98% at room temperature, a magnetic bar is added and placed in a grill with stirring for 10 minutes. Subsequently, 20 g of ore graphite, having been ground to a fineness of less than 150 microns, is added and continuously stirred for 10 minutes and then added slowly 120 grams of potassium permanganate, the temperature is raised to 65 C. and left stirring for 8 hours. After the reaction mixture is transferred to a beaker of 4 liters containing 2 liters of bi-distilled water previously frozen and subsequently 15 ml of hydrogen peroxide to 30% are added again and allowed to stir at room temperature for 30 minutes. Let stand for 20 hours. The supernatant was stored and decanted material is transferred to centrifuge tubes and centrifuged at 4500 rpm for 15 minutes. The solid obtained is transferred to a beaker and bi-distilled water is added and stirring is maintained for one hour and allowed to stand for 20 hours, and the rest and above procedure is repeated centrifugation until the pH of the decanted solution around 3 to 4 (measured with digital pH meter). The solid thus obtained is graphite oxide from ore graphite.

[0046] To obtain graphene oxide, the graphite oxide was subjected to an ultrasonic treatment at room temperature for 270 minutes. That time is required for delamination and formation of the corresponding graphene oxide.