A METHOD FOR THE MANUFACTURE OF REDUCED GRAPHENE OXIDE FROM KISH GRAPHITE

Abstract

A method for the manufacture of reduced graphene oxide from Kish graphite including the pretreatment of kish graphite, the oxidation of pre-treated kish graphite into graphene oxide and the reduction of graphene oxide into reduced graphene oxide, the reduced graphene oxide and the use of the graphene oxide.

Claims

1-17. (canceled)

18. A method for manufacture of reduced graphene oxide from kish graphite comprising: A. providing kish graphite, B. pre-treating the kish graphite including the following successive sub-steps: i. a sieving step wherein the kish graphite is classified by size as follows: a) kish graphite having a size below 50 μm, b) kish graphite having a size above or equal to 50 μm,  the fraction a) of kish graphite having a size below 50 μm being removed, ii. a flotation step with the fraction b) of kish graphite having a size above or equal to 50 μm and iii. an acid leaching step wherein an acid is added so that a ratio in weight (acid amount)/(kish graphite amount) is between 0.25 and 1.0, C. oxidizing the pre-treated kish-graphite obtained after step B) in order to obtain graphene oxide including the following successive sub-steps: i. preparation of a mixture including the pre-treated kish-graphite, an acid and ammonium nitrate (NH.sub.4NO.sub.3), the mixture being kept at a temperature below 5° C., ii. addition of an oxidizing agent into the mixture obtained in step C.i), iii. after a targeted level of oxidation is reached, addition of a chemical element to stop the oxidation reaction, iv. optionally, separation of graphite oxide from the mixture obtained in step C.iii) and v. exfoliation of the graphite oxide from the mixture obtained in step C.iii) into graphene oxide, and D. reducing of the graphene oxide into reduced graphene oxide.

19. The method as recited in claim 18 wherein in step B.i), a fraction a) of kish graphite having a size below 55 μm is removed and in step B.ii), a fraction b) of kish graphite has a size above or equal to 55 μm.

20. The method as recited in claim 19 wherein in steps B.i) and B.ii), the fraction b) of kish graphite has a size below or equal to 300 μm, any fraction of kish graphite having a size above 300 μm being removed before step B.ii)

21. The method as recited in claim 18 wherein in step B.iii), the acid amount/kish graphite amount ratio in weight is between 0.25 and 0.9.

22. The method as recited in claim 18 wherein in step B.iii), the acid is selected from the group consisting of the following elements: chloride acid, phosphoric acid, sulfuric acid, nitric acid and a mixture thereof.

23. The method as recited in claim 18 wherein in step C.ii), the oxidizing agent is chosen from the group consisting of: potassium permanganate (KMnO.sub.4), H.sub.2O.sub.2, O.sub.3, H.sub.2S.sub.2O.sub.8, H.sub.2SO.sub.5, KNO.sub.3, NaClO and a mixture thereof.

24. The method as recited in claim 18 wherein in step C.iii), the chemical element used to stop the oxidation reaction is chosen from the group consisting of: an acid, non-deionized water, deionized water, H.sub.2O.sub.2 and a mixture thereof.

25. The method as recited in claim 24 wherein the chemical element and a further chemical element chosen from the group are used to stop the oxidation reaction, the element and the further chemical element being used successively.

26. The method as recited in claim 24 wherein the chemical element and a further chemical element chosen from the group are used to stop the oxidation reaction, the element and the further chemical element being used simultaneously.

27. The method as recited in claim 18 wherein in step C.iii), the mixture obtained in step C.ii) is gradually pumped into the element used to stop the oxidation reaction.

28. The method as recited in claim 18 wherein in step C.vii), the exfoliation is performed by using ultrasound or thermal exfoliation.

29. The method as recited in claim 18 wherein step C.iv) is performed and the graphite oxide is separated by centrifugation, by decantation or filtration.

30. The method as recited in claim 18 wherein in step C.i), the acid is selected from the group consisting of the following elements: chloride acid, phosphoric acid, sulfuric acid, nitric acid and a mixture thereof.

31. The method as recited in claim 18 wherein in step D) includes the following sub-steps: i. reduction of graphene oxide to reduced graphene oxide with a reducing agent, ii. agitation of the mixture obtained in step D.i), iii. optionally, washing of the reduced graphene oxide and iv. optionally, drying of the reduced graphene oxide.

31. The method as recited in claim 31 wherein in step D.i), the reducing agent is chosen from the group consisting of: acid ascorbic; urea; hydrazine hydrate; alkaline solution such as NaOH or KOH; phenols such as gallic acid, tannin acid, dopamine or tea polyphenol; alcohols such as methyl alcohol, ethyl alcohol or isopropyl alcohol; glycine; sodium citrate and sodium borohydride.

32. The method as recited in claim 21 wherein in step D.ii), the mixture is kept at a temperature between 50 and 120° C.

33. The method as recited in claim 21 wherein in step D.ii), the agitation is performed during less than 24 hours.

34. Reduced Graphene oxide comprising below 20% by weight of oxygen functional groups and having an average lateral size below 30 μm including at least one layer sheet obtainable from the method as recited in claim 18.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] To illustrate the invention, various embodiments and trials of non-limiting examples will be described, particularly with reference to the following Figures:

[0039] FIG. 1 illustrates an example of one layer of reduced graphene oxide according to the present invention.

[0040] FIG. 2 illustrates an example of a few layers of reduced graphene oxide according to the present invention.

DETAILED DESCRIPTION

[0041] The invention relates to a method for the manufacture of reduced graphene oxide from kish graphite comprising: [0042] A. the provision of kish graphite, [0043] B. a pre-treatment step of said kish graphite comprising the following successive sub-steps: [0044] i. a sieving step wherein the kish graphite is classified by size as follows: [0045] a) kish graphite having a size below 50 μm, [0046] b) kish graphite having a size above or equal to 50 μm, the fraction a) of kish graphite having a size below 50 μm being removed, [0047] ii. a flotation step with the fraction b) of kish graphite having a size above or equal to 50 μm and [0048] iii. an An acid leaching step wherein an acid is added so that the ratio in weight (acid amount)/(kish graphite amount) is between 0.25 and 1.0, [0049] C. an oxidation step of the pre-treated kish-graphite obtained after step B) in order to obtain graphene oxide comprising the following successive sub-steps: [0050] i. the preparation of a mixture comprising the pre-treated kish-graphite, an acid and ammonium nitrate (NH.sub.4NO.sub.3), the mixture being kept at a temperature below 5° C., [0051] ii. the addition of an oxidizing agent into the mixture obtained in step C.i), [0052] iii. after the targeted level of oxidation is reached, the addition of an element to stop the oxidation reaction, [0053] iv. optionally, the separation of graphite oxide from the mixture obtained in step C.iii) and [0054] v. the exfoliation of graphite oxide into graphene oxide [0055] D. a reduction of graphene oxide into reduced graphene oxide.

[0056] Without willing to be bound by any theory, it seems that the method according to the present invention allows for the production of reduced graphene oxide having good quality from high purity pre-treated Kish graphite. Indeed, the Kish graphite obtained after step B) has a purity of at least 90%. Moreover, the method including the pre-treatment of kish graphite, the oxidation into graphene oxide and the reduction of graphene oxide is easy to implement at industrial scale and is less polluting than methods of the prior art, in particular the one using NaNO.sub.3. Indeed, on the one hand, it is believed that the no toxic gases produced during the oxidation are N.sub.2, O.sub.2 and H.sub.2O with NH.sub.4NO.sub.3 instead of NO.sub.2, N.sub.2O.sub.4 and NH.sub.3 with NaNO.sub.3. On the other hand, the amount of gases produced with NH.sub.4NO.sub.3 is higher than the one produced with NaNO.sub.3. Thus, more gases are intercalated between the kish graphite layers so that during the oxidation step C.ii), KMnO.sub.4 can easily navigate between the kish graphite layers and oxidize them. It results in a significant reduction of the oxidation time compared to NaNO.sub.3.

[0057] Preferably, in step A), the Kish graphite is a residue of the steelmaking process. For example, it can be found in a blast furnace plant, in an iron making plant, in the torpedo car and during ladle transfer.

[0058] In step B.i), the sieving step can be performed with a sieving machine.

[0059] After the sieving, the fraction a) of Kish graphite having a size below 50 μm is removed. Indeed, without willing to bound by any theory, it is believed that the kish graphite having a size below 50 μm contains a very small quantity of graphite, for example less than 10%.

[0060] Preferably in step B.ii), the flotation step is performed with a flotation reagent in an aqueous solution. For example, the flotation reagent is a frother selected from among: methyl isobutyl carbinol (MIBC), pine oil, polyglycols, xylenol, S-benzyl-S′-n-butyl trithiocarbonate, S,S′-dimethyl trithiocarbonate and S-ethyl-S′-methyl trithiocarbonate. Advantageously, the flotation step is performed using a flotation device.

[0061] Preferably, in step B.i), the fraction a) of kish graphite having a size below 55 μm is removed and in step B.ii), the fraction b) of kish graphite has a size above or equal to 55 μm. More preferably, in step B.i), the fraction a) of kish graphite having a size below 60 μm is removed and wherein in step B.ii), the fraction b) of kish graphite has a size above or equal to 60 μm.

[0062] Preferably, in steps B.i) and B.ii), the fraction b) of kish graphite has a size below or equal to 300 μm, any fraction of kish graphite having a size above 300 μm being removed before step B.ii).

[0063] More preferably in steps B.i) and B.ii), the fraction b) of kish graphite has a size below or equal to 275 μm, any fraction of kish graphite having a size above 275 μm being removed before step B.ii).

[0064] Advantageously, in steps B.i) and B.ii), the fraction b) of kish graphite has a size below or equal to 250 μm, any fraction of kish graphite having a size above 250 μm being removed before step B.ii).

[0065] In step B.iii), the (acid amount)/(kish graphite amount) ratio in weight is between 0.25 and 1.0, advantageously between 0.25 and 0.9, more preferably between 0.25 and 0.8. For example, the (acid amount)/(kish graphite amount) ratio in weight is between 0.4 and 1.0, between 0.4 and 0.9 or between 0.4 and 1. Indeed, without willing to be bound by any theory, it seems that if the (acid amount)/(kish graphite amount) ratio is below the range of the present invention, there is a risk that the kish graphite comprises a lot of impurities. Moreover, it is believed that if the (acid amount)/(kish graphite amount) ratio is above the range of the present invention, there is a risk that a huge amount of chemical waste is generated.

[0066] Preferably, in step B.iii), the acid is selected among the following elements: chloride acid, phosphoric acid, sulfuric acid, nitric acid or a mixture thereof.

[0067] Then, optionally, the kish graphite is washed and dried.

[0068] The pre-treated Kish graphite obtained after step B) of the method according to the present invention has a size above or equal to 50 μm. The pre-treated Kish graphite has a high purity, i.e. at least of 90%. Moreover, the degree of crystallinity is improved compared to conventional methods allowing higher thermal and electrical conductivities and therefore higher quality.

[0069] In step C.i), the pre-treated kish graphite is mixed with an acid and ammonium nitrate (NH.sub.4NO.sub.3). Preferably in step C.i), the acid is selected among the following elements: chloride acid, phosphoric acid, sulfuric acid, nitric acid or a mixture thereof. In a preferred embodiment, the mixture comprises the pre-treated kish-graphite, sulfuric acid and ammonium nitrate.

[0070] Preferably in step C.ii), the oxidizing agent is chosen from: potassium permanganate (KMnO.sub.4), H.sub.2O.sub.2, O.sub.3, H.sub.2S.sub.2O.sub.8, H.sub.2SO.sub.5, KNO.sub.3, NaClO or a mixture thereof. In a preferred embodiment, the oxidizing agent is potassium permanganate.

[0071] Then, in step C.iii), when the targeted level of oxidation is reached, a chemical element is added to stop the oxidation. The targeted level of oxidation depends on the oxidation degree of graphene oxide, i.e. having at least 45% by weight of oxygen groups according to the present invention. The level of oxidation of graphene oxide can be analyzed by scanning electron microscopy (SEM), X ray diffraction spectroscopy (XRD), Transmission electron microscopy (TEM), LECO analysis and/or Raman spectroscopy over time during the oxidation.

[0072] Then, advantageously in step C.iii), the chemical element used to stop the oxidation reaction is chosen from: an acid, non-deionized water, deionized water, H.sub.2O.sub.2 or a mixture thereof.

[0073] In a preferred embodiment, when at least two elements are used to stop the reaction, they are used successively or simultaneously. Preferably, deionized water is used to stop the reaction and then H.sub.2O.sub.2 is used to eliminate the rest of the oxidizing agent. In another preferred embodiment, H.sub.2O.sub.2 is used to stop the reaction and eliminate the rest of the oxidizing agent. In another preferred embodiment, H.sub.2O.sub.2 is used to stop the reaction by this following reaction:

2KMnO.sub.4+3H.sub.2O.sub.2=2MnO.sub.2+3O.sub.2+2KOH+2H.sub.2O.

[0074] Then, to eliminate MnO.sub.2, an acid can be used. For example, HCl is added to the mixture so that the following reaction happens:

MnO.sub.2+2HCl=MnCl.sub.2 (soluble in water)+H.sub.2O.

[0075] Without willing to be bound by any theory, it seems that when the element to stop the reaction is added into the mixture, there is a risk that this addition is too exothermic resulting in explosion or splashing. Thus, preferably in step C.iii), the element used to stop the reaction is slowly added into the mixture obtained in step C.ii). More preferably, the mixture obtained in step C.ii) is gradually pumped into the element used to stop the oxidation reaction. For example, the mixture obtained in step C.ii) is gradually pumped into deionized water to stop the reaction.

[0076] In step C.iv), graphite oxide is separated from the mixture obtained in step C.iii). Preferably, the graphite oxide is separated by centrifugation, by decantation or filtration.

[0077] Then, optionally, the graphite oxide is washed. For example, the graphite oxide is washed with an element chosen from among: deionized water, non-deionized water, an acid or a mixture thereof. For example, the acid is selected among the following elements: chloride acid, phosphoric acid, sulfuric acid, nitride acid or a mixture thereof.

[0078] After, optionally, the graphite oxide is dried, for example with air or at high temperature in the vacuum condition.

[0079] Preferably in step C.v), the exfoliation is performed by using ultrasound or thermal exfoliation. Preferably, the mixture obtained in step C.iii) is exfoliated into one or a few layers of graphene oxide.

[0080] After step C), Graphene oxide comprising at least 45% by weight of oxygen functional groups and having an average lateral size between 5 and 50 μm, preferably between 10 and 40 μm and more preferably between 10 and 30 μm comprising at least one layer sheet is obtained.

[0081] Then, preferably, in step D), the graphene oxide is partially or completely reduced in order to obtain a reduced graphene oxide having from 0.4% to 25% by weight, more preferably from 1 to 20% of oxygen groups.

[0082] Preferably, step D) comprises the following sub-steps: [0083] i. The reduction of graphene oxide with a reducing agent, [0084] ii. agitation of the mixture obtained in step D.i), [0085] iii. optionally, the washing of the reduced graphene oxide and [0086] iv. optionally, the drying of the reduced graphene oxide.

[0087] In step D.i), preferably, the reducing agent is chosen from: acid ascorbic; urea; hydrazine hydrate; alkaline solution such as NaOH or KOH; phenols such as gallic acid, tannin acid, dopamine or tea polyphenol; alcohols such as methyl alcohol, ethyl alcohol or isopropyl alcohol; glycine; sodium citrate or sodium borohydride. More preferably, the reducing agent is acid ascorbic since the ascorbic acid is more environmentally friendly.

[0088] Advantageously, in step D.ii), the mixture is kept at a temperature between 50 and 120° C., more preferably between 60 and 95° C. and advantageously between 80 and 95° C. Preferably, the agitation is performed during less 24 hours, more preferably during less than 15 hours and advantageously during 1 to 10 hours.

[0089] By applying the method according of the present invention, reduced graphene oxide comprising below 20% by weight of oxygen functional groups and having an average lateral size below 30 μm preferably below 20 μm and more preferably below 10 μm comprising at least one layer sheet is obtained.

[0090] FIG. 1 illustrates an example of one layer of reduced graphene oxide according to the present invention. The lateral size means the highest length of the layer through the X axis, the thickness means the height of the layer through the Z axis and the width of the nanoplatelet is illustrated through the Y axis.

[0091] FIG. 2 illustrates an example of a few layers of reduced graphene oxide according to the present invention. The lateral size means the highest length of the layer through the X axis, the thickness means the height of the layer through the Z axis and the width of the nanoplatelet is illustrated through the Y axis.

[0092] Preferably, reduced graphene oxide is deposited on metallic substrate steel to improve some properties such as corrosion resistance of a metallic substrate.

[0093] In another preferred embodiment, reduced graphene oxide is used as cooling reagent. Indeed, graphene oxide can be added to a cooling fluid. Preferably, the cooling fluid can be chosen from among: water, ethylene glycol, ethanol, oil, methanol, silicone, propylene glycol, alkylated aromatics, liquid Ga, liquid In, liquid Sn, potassium formate and a mixture thereof. In this embodiment, the cooling fluid be used to cool down a metallic substrate. For example, the metallic substrate is selected from among: aluminum, stainless steel, copper, iron, copper alloys, titanium, cobalt, metal composite, nickel.

[0094] The invention will now be explained in trials carried out for information only. They are not limiting.

Examples

[0095] Trials 1, 2 and 3 were prepared by providing Kish graphite from steelmaking plant. Then, Kish graphite was sieved to be classified by size as follows:

[0096] a) Kish graphite having a size below <63 μm and [0097] b) Kish graphite having a size above or equal to 63 μm.
The fraction a) of Kish graphite having a size below 63 μm was removed.

[0098] For Trials 1 and 2, a flotation step with the fraction b) of Kish graphite having a size above or equal to 63 μm was performed. The flotation step was performed with a Humboldt Wedag flotation machine with MIBC as frother. The following conditions were applied: [0099] Cell volume (I): 2, [0100] Rotor speed (rpm): 2000, [0101] Solid concentration (%): 5-10, [0102] Frother, type: MIBC, [0103] Frother, addition (g/T): 40, [0104] Conditioning time (s): 10 and [0105] Water conditions: natural pH, room-temperature.

[0106] All Trials were then leached with the hydrochloric acid in aqueous solution. Trials were then washed with deionized water and dried in air at 90° C.

[0107] After, Trial 1 was mixed with ammonium nitrate and sulfuric acid while Trials 2 and 3 were mixed with sodium nitrate and sulfuric acid in an ice-bath. Potassium permanganate was slowly added into Trials 1 to 3. Then, mixtures were transferred into water bath and kept at 35° C. to oxidize the Kish graphite.

[0108] After the oxidation, Trials were gradually pumped into deionized water.

[0109] For Trial 1, the heat was removed and H.sub.2O.sub.2 in aqueous solution was added until there was no gas producing. MnO.sub.2 was produced. Then, HCl was added to the mixture to eliminate MnO.sub.2.

[0110] For Trials 2 and 3, After stopping the oxidation reaction, the heat was removed and H.sub.2O.sub.2 in aqueous solution was added until there was no gas producing and mixtures were stirred to eliminate the rest of H.sub.2O.sub.2.

[0111] Then, for all Trials, Graphite oxide was separated from the mixture by decantation. They were exfoliated using ultrasound in order to obtain one or two layer(s) of graphene oxide. Finally, graphene oxide was separated from the mixture by centrifugation, washed with water and dried with air.

[0112] L-ascorbic acid were mixed with aqueous solutions of Trials 1 to 3. The reaction mixtures were agitated at 90° C. to reduce the graphene oxide sheets. All Trials were then washed and dried to obtain reduced graphene oxide powder.

[0113] Graphene oxide and Reduced graphene oxide were analyzed by scanning electron microscopy (SEM), X ray diffraction spectroscopy (XRD), Transmission electron microscopy (TEM), LECO analysis and Raman spectroscopy.

[0114] Trials 2 and 3 correspond respectively to Trials 1 and 2 of WO2018178845. Table 1 shows the results obtained.

TABLE-US-00001 Trial 2 Trial 3 Method Trial 1 * (Trial 1 of WO2018178845) (Trial 2 of WO2018178845) Origin of Kish graphite Steelmaking plant Steelmaking plant Steelmaking plant Pre- Sieving step Done, Kish graphite having a Done, Kish graphite having a size Done, Kish graphite having a size treatment size above or equal to 63 μm above or equal to 63 μm kept above or equal to 63 μm kept of Kish kept graphite Flotation step Done Done Not done Acid leaching Done with HCl, (the acid Done with HCl, (the acid Done with HCl, (the acid step amount)/(kish graphite amount)/(kish graphite amount) amount)/(kish graphite amount) amount) ratio in weight is of ratio in weight is of 0.78 ratio in weight is of 1.26 0.78 Pre-treated kish graphite 95% 95% 74.9% purity Oxidation preparation Done with H.sub.2SO.sub.4 and NH.sub.4NO.sub.3 Done with H.sub.2SO.sub.4 and NH.sub.4NO.sub.3 Done with H2SO.sub.4 and NH.sub.4NO.sub.3 step of the mixture Gases N2, O2 and H2O NO2, N2O4 and NH3 NO2, N2O4 and NH3 produced Addition of KMnO.sub.4 KMnO.sub.4 KMnO.sub.4 an oxidizing agent Oxidation 1 h 30 min 3 hours 3 hours time Element to Water followed by H.sub.2O.sub.2 Water followed by H.sub.2O.sub.2 Water followed by H.sub.2O.sub.2 stop the reaction Exfoliation Ultrasound Ultrasound Ultrasound Graphene oxide Graphene oxide comprising Graphene oxide comprising 40% of Graphene oxide comprising 30% of 49% of oxygen groups and oxygen groups and having an oxygen groups and having an having an average Lateral size average Lateral size from 20 to 35 average lateral size from 20 to 35 from 10 to 20 μm with purity of μm with purity of 99.5% μm with purity of 99.0% 99.5% Reduction step Done with acid ascorbic during Done with acid ascorbic during 3 Done with acid ascorbic 3 hours hours during 3 hours Reduced graphene oxide Reduced Graphene oxide Reduced Graphene oxide Reduced Graphene oxide comprising 17% of oxygen comprising 15% of oxygen comprising 15% of oxygen groups groups and having an average groups and having an average and having an average Lateral size Lateral size from 15 to 30 μm Lateral size from 20 to 30 μm with from 20 to 30 μm with purity of 99.5% and an average purity of 99.5% and an average 99.0% and an average thickness thickness of 1-6 nm thickness of 1-6 nm of 1-6 nm * according to the present invention

[0115] The method of Trial 1 is more environmentally friendly than the method used for Trials 2 and 3. Moreover, the oxidation time with the method of Trial 1 is divided by two. Finally, the reduced graphene oxide obtained with Trial 1 has a high quality.