CN102757042A - Method for preparing thin-layer graphene by liquid chemical method - Google Patents
Method for preparing thin-layer graphene by liquid chemical method Download PDFInfo
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- CN102757042A CN102757042A CN2012102711969A CN201210271196A CN102757042A CN 102757042 A CN102757042 A CN 102757042A CN 2012102711969 A CN2012102711969 A CN 2012102711969A CN 201210271196 A CN201210271196 A CN 201210271196A CN 102757042 A CN102757042 A CN 102757042A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 92
- 239000010439 graphite Substances 0.000 claims abstract description 92
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000009830 intercalation Methods 0.000 claims description 32
- 230000002687 intercalation Effects 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000004220 aggregation Methods 0.000 claims description 10
- 230000002776 aggregation Effects 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- -1 graphite alkene Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000003776 cleavage reaction Methods 0.000 description 8
- 230000007017 scission Effects 0.000 description 8
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
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- 230000033116 oxidation-reduction process Effects 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing thin-layer graphene by a liquid chemical method. The method comprises the following steps of: (1) leading hybrid reaction of a graphite original material with peroxide and concentrated sulfuric acid or fuming sulfuric acid to prepare sulfuric acid intercalated graphite; (2) performing microwave treatment on the sulfuric acid intercalated graphite to form a vermicular graphene accumulate body, and then performing ultrasonic processing to obtain thin-layer graphite; (3) leading reaction of the thin-layer graphite and metal chloride to obtain metal chloride intercalated thin-layer graphite; and (4) leading hybrid reaction of the metal chloride intercalated thin-layer graphite and nonvolatile strong acid, and performing ultrasonic processing on a reaction product to obtain the thin-layer graphene. Preferably, the method also comprises the following step of: (5) dispersing the thin-layer graphene in a solvent to form a graphene dispersion liquid. By the method, the high-quality thin-layer graphene can be prepared at a low cost and on a large scale, and the method is environment-friendly and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of grapheme material, relate in particular to the method that a kind of liquid phase chemical is equipped with a large amount of high quality Graphenes.
Background technology
Graphene caused the very big interest of scientific circles immediately, and has become one of the most popular in recent years material since being found first in 2004, also therefore obtained Nobel Prize in physics in 2010.The electric transmission speed that Graphene is high because of its particular structure has; And be the highest material of known physical strength; Simultaneously stable, transparent, the HS of its chemical property, thermal conductivity are good, therefore store and prepare composite all has extremely tempting application prospect at nano electron device, gas sensor, energy.The preparation of Graphene is the hot issue that people pay close attention to always, because this has been directly connected to the subsequent applications of material.
The preparation method of graphene of having reported at present has: micromechanics is peeled off method, epitaxial growth method, chemical vapour deposition, oxidation-reduction method, solvent and is peeled off method and liquid-phase catalysis reaction method.First three methods is difficult to be applied in the scale operation of Graphene because of its cost height, complicated operation, productive rate hang down.Oxidation-reduction method is with its less cost and realize that easily the advantage of mass-producing becomes the best approach of preparation Graphene, and can prepare stable graphene suspension, has solved Graphene and has been difficult for the dispersive problem.The unique shortcoming of oxidation-reduction method is that the Graphene of preparation exists certain defective; For example; The textural defect of topological defect such as five-ring, seven-membered ring or existence-OH group, the loss that these will cause Graphene part electric property is restricted the application of Graphene.Solvent is peeled off method can prepare high-quality Graphene; The process that whole liquid phase is peeled off is not introduced any defective on the surface of Graphene; For its application in fields such as microtronics, multifunctional composites provides wide application prospect; But it is very low that its shortcoming is a productive rate, limits its commercial applications.And the liquid phase chemical catalysis method just can overcome the Van der Waals force between layer and the layer because need a large amount of catalytic substrates, causes cost very high.So,, prepare the large-area Graphene of high quality in a large number with low cost and be still a challenge at present for the scientific research personnel.
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.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of metal chloride intercalation thin layer graphite among the embodiment 1;
Fig. 2 is the scanning electron microscope diagram of Graphene among the embodiment 1.
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.
Claims (10)
1. a liquid phase chemical prepares the method for thin layer Graphene, it is characterized in that this method 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.
2. liquid phase chemical according to claim 1 prepares the method for thin layer Graphene, it is characterized in that, graphite raw material is selected from any one in natural graphite powder, crystalline graphite powder, graphous graphite powder and the expanded graphite powder at least described in the step (1).
3. liquid phase chemical according to claim 1 prepares the method for thin layer Graphene, it is characterized in that, superoxide comprises ydrogen peroxide 50 described in the step (1).
4. liquid phase chemical according to claim 1 prepares the method for thin layer Graphene, it is characterized in that, metal chloride is selected from iron(ic)chloride at least described in the step (3), cupric chloride, aluminum chloride, nickelous chloride, Repone K, any one in sodium-chlor and the zinc chloride.
5. prepare the method for thin layer Graphene according to claim 1 or 4 described liquid phase chemicals, it is characterized in that, 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.
6. liquid phase chemical according to claim 1 prepares the method for thin layer Graphene, it is characterized in that, the condition of said supersound process is: ultrasonic power 10 W ~ 1500 W, ultrasonic time 2 min ~ 12 h.
7. liquid phase chemical according to claim 1 prepares the method for thin layer Graphene, it is characterized in that, 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.
8. liquid phase chemical according to claim 7 prepares the method for thin layer Graphene; It is characterized in that the method for 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.
9. prepare the method for thin layer Graphene according to each described liquid phase chemical among claim 1-6, the 6-8, it is characterized in that 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.
10. prepare the method for thin layer Graphene according to each described liquid phase chemical among the claim 1-9, it is characterized in that, the arbitrary step in step in this method (1)-(4) is that cycle repeats is more than twice.
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