CN115231559A - Graphene, preparation method thereof and graphene water-based dispersion - Google Patents
Graphene, preparation method thereof and graphene water-based dispersion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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Abstract
The invention discloses a preparation method of graphene, which comprises the following steps: (1) Graphite powder, concentrated sulfuric acid, potassium permanganate powder, hydrogen peroxide, concentrated hydrochloric acid and deionized water are used as raw materials to prepare acidic multi-impurity graphene oxide dispersion liquid, and alkaline solution is added to adjust the pH value; (2) Adding carbonate or bicarbonate into the multi-impurity graphene oxide dispersion liquid, and stirring for reaction to obtain the multi-impurity graphene dispersion liquid; (3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) through reduced pressure distillation, and then slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until the number of crystals is not increased any more, and stopping adding the non-aqueous solvent; (4) And (4) removing the crystal and the nonaqueous solvent in the mixed solution obtained in the step (3) to obtain the graphene. The preparation method can prepare graphene with fewer defects and higher quality; the graphene water-based dispersion prepared by mixing the graphene and the surfactant has good dispersion stability, and can improve the compatibility of the graphene water-based dispersion in an application system.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to graphene, a preparation method thereof and a graphene water-based dispersion obtained by using the graphene.
Background
Carbon is an element existing in a world in a rich form, and the application universality and diversity of carbon have been discovered and valued by people for a long time. The carbon nano material is a carbon material with at least one dimension of a disperse phase being less than 100 nm. With the continuous development of science and technology, carbon nanomaterials are gradually showing irreplaceable important roles in the production and life of human beings.
Graphene carbon nanomaterials discovered in 2004 by a.geim and k.novoselov are single-layer planar materials with two-dimensional honeycomb lattice structures formed by tightly connecting carbon atoms, and are cut and wrapped to form fullerenes, curled to form carbon nanotubes, and overlapped to form graphite. Graphene with a structure similar to that of aromatic hydrocarbon has low chemical property activity, is difficult to disperse and is easy to agglomerate due to the influence of pi-pi bonds, so that the development and application of graphene are greatly limited. The graphene can be prepared in a variety of ways, such as micro-mechanical lift-off, liquid-phase lift-off, chemical vapor deposition and epitaxial growth, and graphene reduction for graphene oxide. The graphene produced by the micro-mechanical stripping method has the highest quality but very low yield, and the prepared graphene is only used for scientific research; the graphene dispersion liquid prepared by the liquid phase stripping method contains few defects of multi-layer graphene, is high in quality, and cannot regulate the number of layers of the graphene; chemical vapor deposition and epitaxial orientation growth methods, which have high requirements on equipment and low raw material conversion rate, and the prepared graphene film is difficult to peel off when attached to a substrate; although the method for preparing graphene by reducing graphene oxide is continuously optimized and improved in actual production as a current scale production method, the formed graphene still has some limitations in high-end application fields. At present, how to prepare graphene with few defects, few layers, high quality and high purity and a graphene dispersion with good dispersibility at low cost is widely researched, and the aim is to better apply the graphene to the fields of textiles, coatings, energy storage and conversion equipment and the like. For example, chinese patent CN105949760B discloses a method for preparing a highly thermally conductive graphene/nylon composite material by adding a graphene oxide dispersion to a nylon monomer, heating and mixing uniformly, and then performing in-situ polymerization by sectional heating; chinese patent CN109666259B discloses a method for preparing modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion, which grafts benzene rigid chemical groups on the surface of graphene, utilizes steric hindrance to reduce van der waals force between graphene, and increases compatibility between graphene and epoxy resin, thereby increasing the dispersion effect of graphene in epoxy paint. The preparation of graphene dispersoids with good dispersion effects is a key technology for realizing the application of the graphene dispersoids in the fields of textiles, coatings, energy storage, conversion equipment and the like, but the existing preparation technology of graphene oxide and the graphene dispersoids has a series of defects of complex operation, low efficiency and the like, and the popularization and application of graphene in the fields are limited.
The preparation and application technology of a large amount of graphene and a dispersion thereof are disclosed at home and abroad, for example, chinese patent CN102066245B discloses a preparation method of a graphene dispersion, and in example 1, the preparation of the graphene is that graphene oxide obtained in Hummer's improved method is purified by dialysis, and is reduced by adding a reducing agent (hydrazine, sodium borohydride and the like) into an alkaline solution after being treated by ultrasonic treatment, centrifugation and the like. In general, the purpose of centrifugation is to remove graphite that has not been exfoliated, but a large amount of equipment and time are required, and the risk of environmental pollution by reducing agents such as hydrazine and sodium borohydride is high. Chinese patent CN102701187B discloses a method for preparing graphene and graphene prepared by using the method, which uses graphite as a raw material, inserts a graphite interlayer compound made of metal between graphite layers, and then strips the compound to prepare graphene. Although the method for preparing graphene is low in cost, the graphene sheet layer obtained by stripping can damage the structure of graphene due to the growth of metal atom disorder, and the application field of graphene is limited by introducing metal. US9950930B2 discloses a method for preparing graphene, which comprises the steps of forming a dispersion liquid from a carbon-based material and a dispersant, continuously passing the dispersion liquid through a high-pressure homogenizer having a microchannel with a micron-sized diameter connected between an inlet and an outlet, and further exfoliating the carbon-based material to form graphene with a nano-sized thickness. In response, korean patent No. 102097814B1 discloses a high pressure homogenizer and a method for manufacturing graphene using the same, in which microchannels in the high pressure homogenizer are described in detail, and specifically, a plurality of first separators in a first flow channel and a plurality of second separators in a second flow channel are included.
The preparation of water-based graphene dispersions often requires the selection of a suitable dispersant system, for example, in the field of coatings, graphene liquid is generally added to the dispersion, which results in the improvement of the hardness, wear resistance, oxidation resistance, curing rate, rheological properties, etc. of the coating, on the one hand, and the achievement of certain specific properties of the coating, such as corrosion resistance, electrical conductivity, flame retardancy, etc., on the other hand. However, the graphene carbon nanomaterial generally has a high specific surface area and is not easy to disperse. Chinese patent CN107010614A discloses a water-based dispersion liquid of carbon nano-materials and a preparation method thereof, and provides a graphene carbon nano-material water-based dispersion liquid with good dispersion stability, which can be prepared by mixing a graphene nano-material, a surfactant and reducing sugar in water, grinding and statically mixing. Chinese patent CN105645387B discloses a graphene dispersant and its application, wherein the dispersant is an aniline oligomer derivative with electrical activity, and can form pi-pi complex with graphene.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide graphene, a method for preparing the same, and a graphene water-based dispersion; the preparation method combines an oxidation-reduction process, an alkali liquor reduction process and a non-aqueous solvent crystallization stripping process to prepare graphene with fewer defects and higher quality; the graphene water-based dispersion prepared by mixing the graphene and the surfactant has good dispersion stability, and can improve the compatibility of the graphene water-based dispersion in an application system.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of graphene comprises the following steps:
(1) Preparing acidic multi-impurity graphene oxide dispersion liquid by taking graphite powder, concentrated sulfuric acid, potassium permanganate powder, hydrogen peroxide, concentrated hydrochloric acid and deionized water as raw materials, adding an alkaline solution into the acidic multi-impurity graphene oxide dispersion liquid, and adjusting the pH value to be more than or equal to 7;
(2) Adding carbonate or bicarbonate into the multi-impurity graphene oxide dispersion liquid obtained in the step (1), and stirring for reaction to obtain the multi-impurity graphene dispersion liquid;
(3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) to 1/10-1/50 of the original volume by reduced pressure distillation, slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until the number of crystals is not increased any more, and stopping adding the non-aqueous solvent;
(4) And (4) removing crystals and a non-aqueous solvent in the mixed solution obtained in the step (3) through layering, filtering, washing and drying to obtain pure graphene.
Further, in the step (1), the specific preparation process of the acidic multi-impurity graphene oxide dispersion liquid is as follows: adding dried graphite powder into 95-98% concentrated sulfuric acid under a stirring state, continuously and slowly adding potassium permanganate powder under the temperature condition of 2-5 ℃ and the stirring state, heating to 35-40 ℃, keeping the state, stirring for 2-4 hours, transferring the obtained solution into an ice water mixture of deionized water, adding hydrogen peroxide into the water diluent of the obtained solution, and adding concentrated hydrochloric acid after the solution is golden yellow and generated bubbles are gradually dissipated to obtain the acidic multi-impurity graphene oxide dispersion liquid.
Wherein the ratio of the dried graphite powder to the 95-98% concentrated sulfuric acid is 1 (w/v).
Further, the concentration of the hydrogen peroxide is more than or equal to 25 percent, and preferably is 30 percent; the concentration of concentrated hydrochloric acid is more than or equal to 35 percent, preferably 35 to 37 percent.
Furthermore, the graphite powder is flaky, has the purity of more than or equal to 95 percent, the mesh number of 500-1200 meshes and the water content of less than 0.1 percent.
Further, the alkaline solution is an aqueous solution formed by one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate and deionized water or distilled water, and the concentration of the aqueous solution is 1-3 mol/L.
Further, the reaction temperature in the step (2) is 60-95 ℃, and preferably 80-90 ℃; the reaction time is 120-180 min.
Further, the carbonate is ammonium carbonate, and the bicarbonate is one of potassium bicarbonate, sodium bicarbonate and ammonium bicarbonate. The carbonate or bicarbonate may be a solid or an aqueous solution.
Further, in the step (3), the reduced pressure distillation is carried out under the temperature condition of 35-45 ℃ and the atmospheric pressure of less than or equal to 0.5 Mpa; the nonaqueous solvent is a solvent such as alcohols, ethers, esters, aromatic hydrocarbons, alicyclic hydrocarbons, etc., and preferably is anhydrous ethanol among alcohols.
And (3) after the distilled water generated in the reduced pressure distillation process is recovered, the distilled water can be used as the cleaning water in the step (4), the subsequent preparation water of the graphene water-based dispersion, and the alkaline solution water, the carbonate solvent or the bicarbonate solvent.
Further, a stirring step may be added between step (3) and step (4), i.e. stirring the graphene mixture containing the non-aqueous solvent and the crystal obtained in step (3) by a low-speed stirring manner, and then standing for a short time, so as to separate out the crystal of the lower layer.
Wherein the cation in the crystal is K + 、Na + 、Mn 2+ And the anion is SO 4- 、Cl - 。
The invention further provides graphene prepared by the preparation method.
The invention further provides a graphene water-based dispersion, which is obtained by uniformly dispersing the graphene prepared by the preparation method and a surfactant in water at a high speed.
Wherein the surfactant comprises an anionic surfactant and a nonionic surfactant; the anionic surfactant is one or the combination of more than two of alkanolamide succinic acid monoester disodium salt, N-lauroyl sarcosine sodium, hexadecyl sodium sulfonate and pyrrolidone carboxylic acid sodium; the nonionic surfactant is one or more of amide surfactant TMA-1, polyoxyethylene sorbitan monopalmitate, nonionic block water-based polyurethane surfactant, isomeric dodecyl polyoxyethylene ether and oleamide.
The beneficial effects of the invention are:
the preparation method provided by the invention combines an oxidation-reduction process, an alkali liquor reduction process and a wastewater solvent crystallization stripping process to prepare graphene with fewer defects and higher quality; the alkali liquor reduction process adopts carbonate or bicarbonate to reduce the graphene oxide, avoids adopting reducing agents such as hydrazine hydrate and the like, reduces environmental pollution and is beneficial to environmental protection; after the alkali liquor reduction process, the graphene dispersion liquid contains various impurity ions (existing in the form of inorganic salt dissolved in water); in the non-aqueous solvent crystallization stripping process, the non-aqueous solvent is added into the concentrated multi-impurity graphene dispersion liquid, so that impurities (dissolved inorganic salt) are instantly crystallized and separated out, and the crystals of the inorganic salt attached to and inserted between graphene layers form an expansion effect, so that the graphene sheets are effectively stripped.
According to the invention, by combining the oxidation-reduction process, the alkali liquor reduction process and the non-aqueous solvent crystallization stripping process, the graphene can be effectively and fully stripped by utilizing the crystallization expansion effect of impurities brought by the oxidation-reduction raw material, and the crystallization impurities can be effectively removed, so that the graphene with few defects and high quality can be obtained on the basis of keeping the graphene structure to the maximum extent.
The graphene water-based dispersion prepared by mixing the high-quality graphene and the surfactant has good dispersion stability, and can improve the compatibility of the graphene water-based dispersion in an application system.
Drawings
Fig. 1 is a microscopic view of the graphene water-based dispersion prepared in example 1 at different magnifications.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of graphene, which comprises the following steps:
(1) Graphite powder, concentrated sulfuric acid, potassium permanganate powder, hydrogen peroxide, concentrated hydrochloric acid and deionized water are used as raw materials to prepare acidic multi-impurity graphene oxide dispersion liquid, then alkaline solution is added into the acidic multi-impurity graphene oxide dispersion liquid, and the pH value is adjusted to be more than or equal to 7.
The specific preparation process of the acidic multi-impurity graphene oxide dispersion liquid comprises the following steps: adding dried graphite powder into 95-98% concentrated sulfuric acid under a stirring state, continuously and slowly adding potassium permanganate powder under the temperature condition of 2-5 ℃ and the stirring state, heating to 35-40 ℃, keeping the state, stirring for 2-4 hours, transferring the obtained solution into an ice-water mixture of deionized water, adding hydrogen peroxide into the water diluent of the obtained solution, and adding concentrated hydrochloric acid after the solution is golden yellow and the generated bubbles are gradually dissipated to obtain the acidic multi-impurity graphene oxide dispersion liquid.
Wherein the ratio of the dried graphite powder to 95-98% concentrated sulfuric acid is 1 (w/v).
The concentration of the hydrogen peroxide is more than or equal to 25 percent, and the preferred concentration is 30 percent; the concentration of concentrated hydrochloric acid is more than or equal to 35 percent, preferably 35 to 37 percent.
The graphite powder is flaky, the purity is more than or equal to 95%, the mesh number is 500-1200 meshes, and the water content is less than 0.1%.
The alkaline solution is an aqueous solution with the concentration of 1-3 mol/L formed by one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate and deionized water or distilled water.
(2) Adding carbonate or bicarbonate into the multi-impurity graphene oxide dispersion liquid obtained in the step (1), and stirring and reacting at the temperature of 60-95 ℃ for 120-180 min to obtain the multi-impurity graphene oxide dispersion liquid; in the step (2), the reaction temperature is preferably 80 to 90 ℃;
the carbonate is ammonium carbonate, and the bicarbonate is one of potassium bicarbonate, sodium bicarbonate and ammonium bicarbonate. The carbonate or bicarbonate may be a solid or an aqueous solution.
(3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) to 1/10-1/50 of the original volume through reduced pressure distillation, slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until the number of crystals is not increased any more, and stopping adding the non-aqueous solvent;
in the step (3), the reduced pressure distillation is carried out under a temperature condition of 35 to 45 ℃ and an atmospheric pressure of 0.5MPa or less. After the distilled water generated in the reduced pressure distillation process is recovered, the distilled water can be used as cleaning water in the step (4), can also be used as subsequent water for preparing the graphene water-based dispersion, and can also be used as water for an alkaline solution, a carbonate solvent or a bicarbonate solvent;
the non-aqueous solvent is a solvent such as alcohols, ethers, esters, aromatic hydrocarbons, alicyclic hydrocarbons, etc., and preferably is absolute ethanol among alcohols.
(4) And (4) removing crystals and a non-aqueous solvent in the mixed solution obtained in the step (3) through layering, filtering, washing and drying to obtain the graphene.
A stirring step may be added between step (3) and step (4), i.e. stirring the graphene mixture containing the non-aqueous solvent and the crystal obtained in step (3) by a low-speed stirring manner, and then standing for a short time, so as to separate out the crystal of the lower layer.
Wherein the cation in the crystal is K + 、Na + 、Mn 2+ And the anion is SO 4- 、Cl - 。
The invention further provides graphene prepared by the preparation method.
The invention further provides a graphene water-based dispersion, which is obtained by uniformly dispersing the graphene prepared by the preparation method and a surfactant in water at a high speed.
Wherein the surfactant comprises an anionic surfactant and a nonionic surfactant; the anionic surfactant is one or the combination of more than two of alkanolamide succinic acid monoester disodium salt, N-lauroyl sarcosine sodium, hexadecyl sodium sulfonate and pyrrolidine ketonic acid sodium; the nonionic surfactant is one or more of acylamino surfactant TMA-1, polyoxyethylene sorbitan monopalmitate, nonionic block water-based polyurethane surfactant, isomeric dodecyl polyoxyethylene ether and oleamide.
Example 1
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round-bottom flask, adding 20g of dried scaly graphite powder with the purity of more than 95% and the mesh number of 500 meshes under the stirring state, cooling a graphite-sulfuric acid mixed solution to 5 ℃, adding 80g of potassium permanganate powder under the stirring state, heating to 40 ℃, stirring for 3 hours, transferring a reaction solution into 2500ml of an ice-water mixture, adding 240ml of 30% hydrogen peroxide, adding 250ml of 37% concentrated hydrochloric acid after the solution becomes golden yellow and bubbles generated gradually dissipate, uniformly stirring, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.0, adding 300g of sodium bicarbonate, heating to 90 ℃, stirring for 120 minutes at constant temperature, cooling to below 40 ℃, distilling the solution at 40 ℃ under reduced pressure to 1/50 of the original volume, continuing to add anhydrous ethanol until the crystals do not increase any more, layering, filtering, drying, removing ethanol in the solution and water washing to obtain pure graphene.
A micrograph of the graphene water-based dispersion shown in fig. 1 at different magnifications; as can be seen from the figure, the graphene is dispersed in water more uniformly.
5.0g of the graphene, 3.0g of a surfactant (sodium pyrrolidone-based carboxylate: isomeric dodecyl alcohol polyoxyethylene ether 1030=1 (w/w)) and 92.0g of water were uniformly dispersed at a high speed to obtain a graphene water-based dispersion.
Example 2
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round-bottom flask, adding 20g of dried scaly graphite powder with the purity of more than 95% and the mesh number of 500 meshes under the stirring state, cooling a graphite-sulfuric acid mixed solution to 5 ℃, adding 75g of potassium permanganate powder under the stirring state, heating to 38 ℃, stirring for 3h, transferring a reaction solution into 2500ml of an ice-water mixture, adding 180ml of 30% hydrogen peroxide, adding 250ml of 37% concentrated hydrochloric acid after the solution becomes golden yellow and generated bubbles gradually dissipate, uniformly stirring, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.5, adding 200g of ammonium carbonate, heating to 90 ℃, stirring for 120min at constant temperature, cooling to below 40 ℃, distilling the solution at 40 ℃ under reduced pressure to 1/40 of the original volume, continuing to add anhydrous ethanol until the crystals do not increase any more, layering, filtering, drying, removing ethanol and crystal substances in the solution, and washing with water to obtain pure graphene.
After 5.0g of the graphene, 3.4g of a surfactant (sodium hexadecylsulfonate: polyoxyethylene sorbitan monopalmitate =0.8 (w/w)) and 91.6g of water were uniformly dispersed at a high speed, a graphene water-based dispersion was obtained.
Example 3
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round bottom flask, adding 20g of dried scaly graphite powder with the purity of more than 95% and the mesh number of 1200 mesh under the stirring state, cooling a graphite-sulfuric acid mixed solution to 4 ℃, adding 70g of potassium permanganate powder under the stirring state, heating to 40 ℃, stirring for 2 hours, transferring a reaction solution into 2500ml of an ice-water mixture, adding 140ml of 30% hydrogen peroxide, adding 250ml of 37% concentrated hydrochloric acid after the solution is golden and generated bubbles are gradually dissipated, uniformly stirring, adding 3mol/L sodium hydroxide aqueous solution until the pH value of the solution is 9.0, adding 350g of potassium bicarbonate, heating to 80 ℃, stirring at constant temperature for 180min, cooling to below 40 ℃, distilling the solution at 35 ℃ under reduced pressure to 1/25 of the original volume, continuing adding absolute ethanol until the crystals are not increased any more, and then stopping adding absolute ethanol, layering, filtering, drying, and washing to remove ethanol and crystalline substances in the solution to obtain pure graphene.
Taking 5.5g of the graphene, 4.0g of a surfactant (alkanolamide succinic acid monoester disodium salt: acylamino surfactant TMA-1= -0.9, 1.1 (w/w)) and 90.5g of water, and uniformly dispersing at a high speed to obtain the graphene water-based dispersion.
Example 4
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round-bottom flask, adding 20g of dried scaly graphite powder with the purity of more than 95% and the mesh number of 1200 mesh under the stirring state, cooling a graphite-sulfuric acid mixed solution to 5 ℃, adding 76g of potassium permanganate powder under the stirring state, heating to 39 ℃, stirring for 3.5h, transferring a reaction solution into 2500ml of an ice-water mixture, adding 220ml of 30% hydrogen peroxide, adding 25037% concentrated hydrochloric acid after the solution becomes golden yellow and bubbles generated gradually dissipate, uniformly stirring, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.5, adding 300g of sodium bicarbonate, heating to 85 ℃, stirring for 150min at constant temperature, cooling to below 40 ℃, distilling the obtained solution under reduced pressure at 40 ℃ to 1/35 of the original volume, continuously adding absolute ethyl alcohol until the crystals do not increase any more, and then stopping adding the absolute ethyl alcohol, layering, filtering, washing, drying and removing the ethyl alcohol and the graphene crystal substances in the solution to obtain the graphite.
The graphene water-based dispersion was obtained by uniformly dispersing 5.5g of the graphene, 4.0g of a surfactant (N-sodium lauroyl sarcosine: non-ionic block water-based polyurethane surfactant = 0.6).
Example 5
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round-bottom flask, adding 20g of dried scaly graphite powder with the purity of more than 95% and the mesh number of 800 meshes under the stirring state, cooling a graphite-sulfuric acid mixed solution to 3 ℃, adding 80g of potassium permanganate powder under the stirring state, heating to 40 ℃, stirring for 3 hours, transferring a reaction solution into 2500ml of an ice-water mixture, adding 200ml of 30% hydrogen peroxide, adding 250ml of 37% concentrated hydrochloric acid after the solution becomes golden yellow and generated bubbles gradually dissipate, uniformly stirring, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.8, adding 350g of potassium bicarbonate, heating to 85 ℃, stirring for 150 minutes at constant temperature, cooling to below 40 ℃, distilling the obtained solution under reduced pressure at 40 ℃ to 1/30 of the original volume, continuing to add anhydrous ethanol until the appeared crystals are not increased any more, layering, filtering, drying, removing ethanol in the solution and water washing to obtain pure graphene.
After 5.2g of the graphene, 3.8g of a surfactant (sodium hexadecylsulfonate: oleamide =1.6 (w/w)) and 91.0g of water were uniformly dispersed at a high speed, a graphene water-based dispersion was obtained.
The graphene prepared by the embodiment has fewer defects and higher quality; and the graphene water-based dispersion prepared by mixing the graphene and the surfactant has good dispersion stability and good compatibility in an application system.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A preparation method of graphene is characterized by comprising the following steps:
(1) Preparing acidic multi-impurity graphene oxide dispersion liquid by taking graphite powder, concentrated sulfuric acid, potassium permanganate powder, hydrogen peroxide, concentrated hydrochloric acid and deionized water as raw materials, and then adding an alkaline solution into the acidic multi-impurity graphene oxide dispersion liquid to adjust the pH value;
(2) Adding carbonate or bicarbonate into the multi-impurity graphene oxide dispersion liquid obtained in the step (1), and stirring for reaction to obtain the multi-impurity graphene dispersion liquid;
(3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) through reduced pressure distillation, and then slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until the number of crystals is not increased any more, and stopping adding the non-aqueous solvent;
(4) And (4) removing crystals and a non-aqueous solvent in the mixed solution obtained in the step (3) through layering, filtering, washing and drying to obtain the graphene.
2. The preparation method of graphene according to claim 1, wherein in the step (1), the specific preparation process of the acidic multi-impurity graphene oxide dispersion liquid is as follows: adding dried graphite powder into 95-98% concentrated sulfuric acid under a stirring state, continuously and slowly adding potassium permanganate powder under the temperature condition of 2-5 ℃ and the stirring state, heating to 35-40 ℃, keeping the state, stirring for 2-4 hours, transferring the obtained solution into an ice-water mixture of deionized water, adding hydrogen peroxide into the water diluent of the obtained solution, and adding concentrated hydrochloric acid after the solution is golden yellow and the generated bubbles are gradually dissipated to obtain the acidic multi-impurity graphene oxide dispersion liquid.
3. The preparation method of graphene according to claim 1 or 2, wherein the concentration of hydrogen peroxide is not less than 25%, and the concentration of concentrated hydrochloric acid is not less than 35%.
4. The preparation method of graphene according to claim 1, wherein the graphite powder is flaky, has a purity of not less than 95%, a mesh number of 500-1200 meshes, and a water content of less than 0.1%.
5. The method according to claim 1, wherein the alkaline solution is an aqueous solution of one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate and deionized water or distilled water at a concentration of 1 to 3 mol/L.
6. The method for preparing graphene according to claim 1, wherein the reaction temperature in the step (2) is 60-95 ℃ and the reaction time is 120-180 min.
7. The method according to claim 1, wherein the carbonate is ammonium carbonate, and the bicarbonate is one of potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate.
8. The method according to claim 1, wherein the vacuum distillation in step (3) is performed at a temperature of 35 to 45 ℃ and an atmospheric pressure of 0.5MPa or less.
9. Graphene produced by the production method according to any one of claims 1 to 8.
10. A graphene water-based dispersion, which is obtained by uniformly dispersing the graphene according to claim 9 and a surfactant in water at a high speed.
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| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
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| JP2011032156A (en) * | 2009-07-06 | 2011-02-17 | Kaneka Corp | Method for manufacturing graphene or thin film graphite |
| US20170096341A1 (en) * | 2015-10-01 | 2017-04-06 | Shandong Yuhuang New Energy Tethnology Co., Ltd | Method of mass producing few-layer graohene powders |
| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
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