Summary of the invention
The objective of the invention is to deficiency of the prior art, a kind of low cost is provided, high quality, a large amount of simultaneously and big area, the eco-friendly liquid phase chemical that is suitable for suitability for industrialized production prepares the method for thin layer Graphene.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of liquid phase chemical prepares the method for thin layer Graphene, and it comprises the steps:
(1) gets graphite raw material and superoxide and the vitriol oil or oleum hybrid reaction, make the sulfuric acid intercalated graphite;
(2) said sulfuric acid intercalated graphite is carried out microwave treatment, form quasiflake graphite alkene aggregation, carry out supersound process again, obtain thin layer graphite;
(3), obtain metal chloride intercalation thin layer graphite with said thin layer graphite and metal chloride reaction;
(4) carry out supersound process with said metal chloride intercalation thin layer graphite and non-volatile strong acid hybrid reaction, and to reaction product, obtain the thin layer Graphene.
Further, graphite raw material described in the step (1) is selected from any one in natural graphite powder, crystalline graphite powder, graphous graphite powder and the expanded graphite powder at least.
Preferably, superoxide comprises ydrogen peroxide 50 described in the step (1).
Metal chloride is selected from iron(ic)chloride at least described in the step (3), cupric chloride, and aluminum chloride, nickelous chloride, Repone K, any one in sodium-chlor and the zinc chloride, but be not limited thereto.
Thin layer graphite and metal chloride are under temperature is 270-500 ℃ condition, to react in the step (3), make metal chloride intercalation thin layer graphite.
Preferably, the condition of said supersound process is: ultrasonic power 10 W ~ 1500 W, ultrasonic time 2 min ~ 12 h.
As one of preferred version, this method specifically comprises the steps:
(1) gets graphite raw material and ydrogen peroxide 50 and the vitriol oil or oleum hybrid reaction, make the sulfuric acid intercalated graphite;
(2) said sulfuric acid intercalated graphite is carried out microwave treatment, form quasiflake graphite alkene aggregation, carry out supersound process again, obtain thin layer graphite;
(3) under temperature is 270-500 ℃ condition,, obtain metal chloride intercalation thin layer graphite with said thin layer graphite and metal chloride reaction;
(4) said metal chloride intercalation thin layer graphite is mixed with the vitriol oil and fully reaction, thereafter reaction product is carried out ultrasonic, cleaning, drying treatment successively, obtain the thin layer Graphene.
The method of drying treatment described in the step (4) is selected from any one or the two or more combinations in vacuum and heating drying, air blast heat drying, freeze-drying, microwave drying and the natural drying at room temperature, but is not limited thereto.
As one of preferred version, this method further comprises following steps:
(5) the thin layer Graphene is scattered in the solvent; Forming concentration is the Graphene dispersion liquid of 0.05 ~ 5 mg/ml; Said solvent is selected from water, N-Methyl pyrrolidone, DMSO 99.8MIN., N at least; Dinethylformamide, 1, any one in 2-ethylene dichloride, neighbour-dichlorobenzene, salicylic aldehyde, Whitfield's ointment, THF, terepthaloyl moietie, glycol ether, pyridine, acetonitrile, ethanol and the methyl alcohol.
Further, the arbitrary steps in step (1)-(4) is that cycle repeats is more than twice in this method.
Compared with prior art, the present invention has following advantage at least:
(1) technology of the present invention is simple, in whole process of preparation, has only adopted sulfuric acid cheap and easy to get, metal chloride and ydrogen peroxide 50 etc. as raw material, and it is auxiliary to need not complex apparatus, and is with low cost, easy handling;
(2) the present invention is under the prerequisite of not destroying graphite-structure, and the chemical process of utilizing of success expands it, and adopts ultrasonic processing technique, does not have in the middle of preventing to react and reunites, and obtains the grapheme material with good physical chemical property.
(3) the present invention prepares the process environment close friend, can not produce objectionable impurities basically, and safety and environmental protection can prepare in enormous quantities, is suitable for suitability for industrialized production.
Embodiment
As previously mentioned, to the problems that prior art exists, this case contriver has proposed technical scheme of the present invention through studying for a long period of time and putting into practice, its can realize the high quality grapheme material low-costly and in high volume, the scale preparation of safety and environmental protection.
As one of preferred scheme, technology of the present invention can comprise the steps:
(1) bulk graphite adopts ydrogen peroxide 50 (concentration can be 30%) and sulfuric acid (concentration can be 98%, perhaps adopts oleum) preparation sulfuric acid intercalated graphite;
(2) microwave obtains expansible thin layer graphite, ultrasonic cleavage, drying;
(3) preparation of thin layer graphite intercalation compound: with metal chloride and thin layer graphite, at high temperature (270-500 ℃) prepares graphite intercalation compound;
(4) liquid phase production expanded graphite: metal chloride intercalation thin layer graphite is put into the vitriol oil, utilizes non-volatile acid to prepare volatile acid, cleavage thin layer graphite;
(5) preparation of high quality Graphene: slightly ultrasonic under mechanical stirring after treating that chemical reaction fully, the clean intercalator carries out drying treatment with the Graphene aqueous dispersions for preparing at last then, can obtain a large amount of high quality graphene powders;
(6) dispersion liquid of high quality Graphene: the Graphene powder of preparation is dispersed in the different solvents, obtains even high quality Graphene dispersion liquid.
Arbitrary step in abovementioned steps (1), (2), (3), (4) or Overall Steps can repeatedly circulate and carry out.
Aforementioned graphite raw material can be selected from natural graphite powder, crystalline graphite powder, graphous graphite powder and expanded graphite powder, but is not limited thereto.
The aforementioned metal muriate can be selected from iron(ic)chloride, cupric chloride, and aluminum chloride, nickelous chloride, Repone K, sodium-chlor, metal chlorides such as zinc chloride, but be not limited thereto.
The condition of aforementioned supersound process is: ultrasonic power 10 W ~ 1500 W, ultrasonic time 2 min ~ 12 h.。
Aforementioned drying process can be selected from vacuum and heating drying, air blast heat drying, freeze-drying, microwave drying, natural drying at room temperature, but be not limited thereto.
Aforementioned solvents can be selected from water, N-Methyl pyrrolidone, DMSO 99.8MIN., N; Dinethylformamide, 1; 2-ethylene dichloride, neighbour-dichlorobenzene, salicylic aldehyde, Whitfield's ointment, THF, terepthaloyl moietie, glycol ether, pyridine, acetonitrile, ethanol, methyl alcohol etc., but be not limited thereto.
The concentration of aforementioned Graphene dispersion liquid is 0.05 ~ 5 mg/ml.
In conjunction with accompanying drawing and some preferred embodiments technical scheme of the present invention is elaborated.But be construed as, the content of the present invention of more clearly explaining not is to be used to limit content of the present invention.
Embodiment 1:
Take by weighing 4 g graphite (325 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g NiCl
2Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of nickelous chloride intercalation, the scanning electron microscope diagram of product is as shown in Figure 1.
Take by weighing 500 mg thin layer graphite intercalation compounds, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.The scanning electron microscope diagram of product is as shown in Figure 2.
Embodiment 2:
Take by weighing 4 g graphite (10 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g FeCl
3Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of iron(ic)chloride intercalation.
Take by weighing 500 mg thin layer graphite intercalation compounds, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.
Embodiment 3:
Take by weighing 4 g graphite (10 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g AlCl
3Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of aluminum chloride intercalation.
Take by weighing 500 mg thin layer graphite intercalation compounds, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.
Embodiment 4:
Take by weighing 4 g graphite (10 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g ZnCl
2Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of zinc chloride intercalation.
Take by weighing 500 mg thin layer graphite intercalation compounds, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.
Embodiment 5:
Take by weighing 4 g graphite (10 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g CuCl
2Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of cupric chloride intercalation.
Take by weighing 500 mg thin layer graphite intercalation compounds, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.
Embodiment 6:
Take by weighing 4 g graphite (10 order), 1 mL ydrogen peroxide 50 is after stirring.Add the oleum contain 20% sulphur trioxide, 30 ℃, stir 1 h after, filter washing, 80 ℃ of baking 4 h.
With the sulfuric acid intercalated graphite residue of above-mentioned oven dry, microwave obtains the quasiflake graphite aggregation, and 500 W power are at n-formyl sarcolysine base pyrrolidone, and ethanol in the acetone and other organic solvent or ultrasonic in the water, obtains the thin layer graphite of cleavage, freeze-drying.
The above-mentioned thin layer graphite that makes is taken by weighing 500 mg, 1.0 g FeCl
3With 1.0 g NiCl
2Place the reaction kettle of 50 ml.And be placed in 300 ℃ the baking oven and react 24h.Prepare the thin layer graphite intercalation compound of iron(ic)chloride and nickelous chloride intercalation.
Take by weighing 500 mg iron(ic)chloride and nickelous chloride binary thin layer graphite intercalation compound, join 200 mL, in 98% the vitriol oil, stir, ultrasonic, clean.Obtain a large amount of Graphenes.
Embodiment shown in more than explanation reaches on drawing can not resolve the design philosophy of the present invention surely of exceeding.In technical field of the present invention, holding identical knowledge the knowledgeable can be with technical thought of the present invention with various form improvement change, and such improvement and change are interpreted as belonging in protection scope of the present invention.