CN115231559B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 162
- 239000006185 dispersion Substances 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000012535 impurity Substances 0.000 claims abstract description 36
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- 239000007788 liquid Substances 0.000 claims abstract description 34
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- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
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- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
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- 238000004821 distillation Methods 0.000 claims abstract description 9
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- 239000000243 solution Substances 0.000 claims description 40
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- 238000000034 method Methods 0.000 claims description 19
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 8
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
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- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
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- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
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- 230000007547 defect Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000001816 cooling Methods 0.000 description 10
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- 238000011946 reduction process Methods 0.000 description 5
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- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 3
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 3
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- 108700004121 sarkosyl Proteins 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- UJGIYHXRNBCGRE-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)[Na] Chemical compound C(CCCCCCCCCCCCCCC)[Na] UJGIYHXRNBCGRE-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
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- 229920001778 nylon Polymers 0.000 description 2
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- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- QAZCPUUJMFBNJO-UHFFFAOYSA-N pyrrolidin-2-one;sodium Chemical compound [Na].O=C1CCCN1 QAZCPUUJMFBNJO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of graphene, which 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, and adding an alkaline solution 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 oxide dispersion liquid; (3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) by reduced pressure distillation, and then slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until crystals are not increased any more, and stopping adding the non-aqueous solvent; (4) And (3) removing the crystals and the nonaqueous solvent in the mixed solution obtained in the step (3) to obtain graphene. The preparation method can prepare graphene with fewer defects and higher quality; the graphene water-based dispersion prepared by mixing the graphene with 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 with a relatively abundant form in the world, and the wide and diverse application of carbon has been found and paid attention to. The carbon nanomaterial refers to a carbon material having a dispersed phase size of at least one dimension less than 100 nm. With the continuous development of technology, carbon nanomaterials are gradually showing an important role of irreplaceability in the production and life of human beings.
The grapheme carbon nanomaterial discovered by A.Geim and K.Novoselov in 2004 is a single-layer planar material with carbon atoms tightly connected with each other to form a two-dimensional honeycomb lattice structure, and the single-layer planar material is cut and wrapped to form fullerene, curled to form carbon nano tubes and overlapped to form graphite. The structure of the graphene is similar to that of aromatic hydrocarbon, and the graphene is low in chemical property activity degree, difficult to disperse and extremely easy to agglomerate due to the influence of pi-pi bonds, so that the development and application of the graphene are greatly limited. There are various preparation methods of graphene, such as micro-mechanical stripping method, liquid phase stripping method, chemical vapor deposition and epitaxial orientation growth method, and graphene preparation method by reduction of graphene oxide. The graphene produced by the micromechanical stripping method has the highest quality but very low yield, and the prepared graphene is only used for scientific research; the multi-layer graphene contained in the graphene dispersion liquid prepared by the liquid phase stripping method has few defects and high quality, but the number of layers of graphene cannot be regulated; the chemical vapor deposition and the epitaxial orientation growth method have high equipment requirements and low raw material conversion rate, and the prepared graphene film is adhered to a substrate and is difficult to strip; the graphene preparation method by reduction of graphene oxide is used as a current mass production method, and although continuous optimization and improvement are still performed in actual production, the formed graphene still has some limitations in the high-end application field. At present, how to prepare graphene with few defects, few layers, high quality and high purity and graphene dispersion with good dispersibility at low cost is widely studied, and aims to better apply the graphene to the fields of spinning, coating, energy storage and conversion equipment and the like. For example, chinese patent CN105949760B discloses a method for preparing a graphene/nylon composite material with high thermal conductivity by adding graphene oxide dispersion into nylon monomer, heating, mixing, and then performing in-situ polymerization by using staged heating; chinese patent CN109666259B discloses a preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid, in which benzene rigid chemical groups are grafted on the surface of graphene, and the steric hindrance effect is utilized to reduce van der waals force between graphene and increase compatibility between graphene and epoxy resin, so as to increase the dispersion effect of graphene in epoxy paint. The preparation of graphene dispersion with good dispersion effect is a key technology for realizing the application of the graphene dispersion in the fields of spinning, coating, energy storage, conversion equipment and the like, however, the existing preparation technology of graphene oxide and graphene dispersion 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.
A large number of graphene and the preparation and application technology of the dispersion thereof are disclosed at home and abroad, for example, chinese patent CN102066245B discloses a preparation method of the graphene dispersion, wherein in the preparation of the graphene in the embodiment 1, graphene oxide obtained in a Hummer's improved method is subjected to dialysis purification, and after treatment modes such as ultrasonic treatment, centrifugation and the like, a reducing agent (hydrazine, sodium borohydride and the like) is added into an alkali solution to reduce the graphene oxide. In general, centrifugation is intended to remove non-exfoliated graphite, but requires a large amount of equipment investment and time investment, and is also associated with a high risk of environmental pollution by reducing agents such as hydrazine and sodium borohydride. Chinese patent CN102701187B discloses a method for preparing graphene and graphene prepared by using the method, in which graphite is used as a raw material, a metal graphite interlayer compound is inserted between graphite layers, and then the compound is peeled off to prepare graphene. Although the method for preparing the graphene is low in cost, the graphene sheets obtained by stripping can grow up due to the disorder of metal atoms to damage the structure of the graphene, and the application field of the graphene is limited by introducing metal. US patent 9950930B2 discloses a preparation method of graphene, which comprises forming a dispersion liquid by a carbon-based material and a dispersing agent, and then continuously passing the dispersion liquid through a high-pressure homogenizer connected with micro-scale diameter micro-channels between inlets and outlets, so as to strip the carbon-based material to form graphene with nano-scale thickness. Accordingly, korean patent No. KR102097814B1 discloses a high-pressure homogenizer and a method of manufacturing graphene using the same, which describe in detail micro-channels in the high-pressure homogenizer, specifically including a plurality of first separators in a first flow channel and a plurality of second separators in a second flow channel.
The preparation of water-based graphene dispersions often requires the selection of a suitable dispersant system according to the requirements of the application system, for example, in the field of coatings, graphene liquid is generally added to the water-based graphene dispersion, so that on one hand the hardness, wear resistance, oxidation resistance, curing rate, rheological property and other properties of the coating are improved, and on the other hand certain special properties such as corrosion resistance, electrical conductivity, flame retardance and the like are obtained. However, the graphene carbon nanomaterial generally has a relatively high specific surface area and is not easy to disperse. Chinese patent CN107010614a discloses a water-based dispersion of carbon nanomaterial and a preparation method thereof, and proposes that graphene nanomaterial, surfactant and reducing sugar can be selected to be mixed in water, and then ground and statically mixed to prepare the water-based dispersion of graphene carbon nanomaterial with good dispersion stability. Chinese patent CN105645387B discloses a graphene dispersing agent and application thereof, the dispersing agent is an aniline oligomer derivative with electrical activity, and is capable of forming pi-pi complex with graphene.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide graphene, a preparation method thereof and a graphene water-based dispersion; the preparation method combines an oxidation-reduction process, an alkali liquor reduction process and a nonaqueous solvent crystallization stripping process to prepare the graphene with fewer defects and higher quality; the graphene water-based dispersion prepared by mixing the graphene with 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 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, and then adding an alkaline solution into the acidic multi-impurity graphene oxide dispersion liquid to adjust 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 multi-impurity graphene oxide 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 crystals are not increased any more, and stopping adding the non-aqueous solvent;
(4) And (3) layering, filtering, washing with water, and drying to remove the crystals and the nonaqueous solvent in the mixed solution obtained in the step (3) to obtain the pure graphene.
Further, in the step (1), the specific preparation process of the acidic multi-impurity graphene oxide dispersion liquid comprises the following steps: adding dry graphite powder into 95-98% concentrated sulfuric acid in a stirring state, continuously and slowly adding potassium permanganate powder at a temperature of 2-5 ℃ under the stirring state, heating to 35-40 ℃, keeping the stirring state for 2-4 hours, transferring the obtained solution into an ice-water mixture of deionized water, adding hydrogen peroxide into a 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.
Wherein, the ratio of the dry graphite powder to the 95-98% concentrated sulfuric acid is 1:25 (w/v), the ratio of the dry graphite powder to the potassium permanganate powder is 1 (3.5-4.0) (w/w), the ratio of the ice-water mixture to the 95-98% concentrated sulfuric acid is 5:1 (v/v), the ratio of the potassium permanganate powder to the hydrogen peroxide is 1 (2-3) (w/v), and the ratio of the concentrated hydrochloric acid to the 95-98% concentrated sulfuric acid is 0.5:1 (v/v).
Further, the concentration of the hydrogen peroxide is more than or equal to 25%, preferably 30%; the concentration of the concentrated hydrochloric acid is more than or equal to 35 percent, preferably 35 to 37 percent.
Further, the graphite powder is flake graphite powder with purity more than or equal to 95%, mesh number between 500 and 1200 mesh and water content less than 0.1%.
Further, 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.
Further, the reaction temperature in the step (2) is 60-95 ℃, 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 solid or aqueous.
In the step (3), the reduced pressure distillation is performed at a temperature of 35 to 45 ℃ and an atmospheric pressure of 0.5Mpa or less; the nonaqueous solvent is a solvent such as alcohols, ethers, esters, aromatic hydrocarbons, or alicyclic hydrocarbons, and preferably is absolute ethanol among alcohols.
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 be used as water for preparing subsequent graphene water-based dispersion, and can also be used as alkaline solution water, carbonate solvent or bicarbonate solvent.
Furthermore, a stirring process can be added between the step (3) and the step (4), namely, the graphene mixture containing the nonaqueous solvent and the crystal obtained in the step (3) is stirred in a low-speed stirring mode and then is left for a short time, so that the crystal of the lower layer part can be separated.
Wherein, in the composition of the crystal, the cation is K + 、Na + 、Mn 2+ And anions are SO 4- 、Cl - 。
The invention further provides graphene, which is prepared by the preparation method.
The invention further provides a graphene water-based dispersion, which is obtained by uniformly dispersing graphene and a surfactant in water at a high speed.
Wherein the surfactant includes an anionic surfactant and a nonionic surfactant; the anionic surfactant is one or more of alkanolamide succinic acid monoester disodium salt, N-lauroyl sarcosine sodium, hexadecyl sodium sulfonate and pyrrolidone sodium carboxylate; the nonionic surfactant is one or more than two of amido surfactant TMA-1, polyoxyethylene sorbitan monopalmitate, nonionic block water-based polyurethane surfactant, isomeric polyoxyethylene decaalcohol ether and oleamide.
The beneficial effects of the invention are as follows:
the preparation method combines an oxidation-reduction process, an alkali liquor reduction process and a wastewater solvent crystallization stripping process to prepare the graphene with fewer defects and higher quality; the alkali liquor reduction process adopts carbonate or bicarbonate to reduce graphene oxide, so that reducing agents such as hydrazine hydrate and the like are avoided, environmental pollution is reduced, and environmental protection is facilitated; after the alkali liquor reduction process, the graphene dispersion liquid contains a plurality of impurity ions (in the form of inorganic salts dissolved in water); in the nonaqueous solvent crystallization stripping process, nonaqueous solvent is added into concentrated multi-impurity graphene dispersion liquid, so that impurities (dissolved inorganic salt) are instantaneously crystallized and separated out, and the crystals of the inorganic salt attached to and inserted between graphene layers form an expansion effect, thereby promoting the effective stripping of graphene sheets.
According to the invention, the oxidation-reduction process, the alkali liquor reduction process and the nonaqueous solvent crystallization stripping process are combined, so that not only can the graphene be effectively and fully stripped by utilizing the crystallization expansion effect of impurities brought by oxidation-reduction raw materials, but also the crystalline impurities can be effectively removed, and the graphene with few defects and high quality can be obtained on the basis of keeping the graphene structure at maximum efficiency.
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 aqueous-based dispersion prepared in example 1 at various magnifications.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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, and then alkaline solution is added into the acidic multi-impurity graphene oxide dispersion liquid to adjust the pH value 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 dry graphite powder into 95-98% concentrated sulfuric acid in a stirring state, continuously and slowly adding potassium permanganate powder at a temperature of 2-5 ℃ under the stirring state, heating to 35-40 ℃, keeping the stirring state for 2-4 hours, transferring the obtained solution into an ice-water mixture of deionized water, adding hydrogen peroxide into a 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.
Wherein, the ratio of the dry graphite powder to the 95-98% concentrated sulfuric acid is 1:25 (w/v), the ratio of the dry graphite powder to the potassium permanganate powder is 1 (3.5-4.0) (w/w), the ratio of the ice-water mixture to the 95-98% concentrated sulfuric acid is 5:1 (v/v), the ratio of the potassium permanganate powder to the hydrogen peroxide is 1 (2-3) (w/v), and the ratio of the concentrated hydrochloric acid to the 95-98% concentrated sulfuric acid is 0.5:1 (v/v).
The concentration of the hydrogen peroxide is more than or equal to 25%, preferably 30%; the concentration of the concentrated hydrochloric acid is more than or equal to 35 percent, preferably 35 to 37 percent.
The graphite powder is flake graphite powder with purity more than or equal to 95%, mesh number between 500 and 1200 mesh and water content less than 0.1%.
The alkaline solution is aqueous solution with 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 for 120-180 min at the temperature of 60-95 ℃ to obtain multi-impurity graphene oxide dispersion liquid; in this 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 solid or aqueous.
(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 crystals are not increased any more, and stopping adding the non-aqueous solvent;
in the step (3), the reduced pressure distillation is performed at a temperature 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 be used as water for preparing subsequent graphene water-based dispersion, and can also be used as alkaline solution water, carbonate solvent or bicarbonate solvent;
among them, the nonaqueous solvent is a solvent such as alcohols, ethers, esters, aromatic hydrocarbons, alicyclic hydrocarbons, etc., preferably absolute ethanol among alcohols.
(4) And (3) layering, filtering, washing with water, and drying to remove the crystals and the nonaqueous solvent in the mixed solution obtained in the step (3) to obtain the graphene.
And (3) a stirring process can be added between the step (3) and the step (4), namely, the graphene mixture containing the nonaqueous solvent and the crystal obtained in the step (3) is stirred in a low-speed stirring mode and then is left for a short time, so that the crystal of the lower layer part can be separated.
Wherein, in the composition of the crystal, the cation is K + 、Na + 、Mn 2+ And anions are SO 4- 、Cl - 。
The invention further provides graphene, which is prepared by the preparation method.
The invention further provides a graphene water-based dispersion, which is obtained by uniformly dispersing graphene and a surfactant in water at a high speed.
Wherein the surfactant includes an anionic surfactant and a nonionic surfactant; the anionic surfactant is one or more of alkanolamide succinic acid monoester disodium salt, N-lauroyl sarcosine sodium, hexadecyl sodium sulfonate and pyrrolidone sodium carboxylate; the nonionic surfactant is one or more than two of amido surfactant TMA-1, polyoxyethylene sorbitan monopalmitate, nonionic block water-based polyurethane surfactant, isomeric polyoxyethylene decaalcohol ether and oleamide.
Example 1
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round bottom flask, adding 20g of dry, scaly, graphite powder with purity higher than 95% and mesh number of 500 meshes into the round bottom flask under stirring, cooling the graphite sulfuric acid mixed solution to 5 ℃, adding 80g of potassium permanganate powder under stirring, heating to 40 ℃, stirring for 3 hours, transferring the reaction solution into 2500ml of ice-water mixture, adding 240ml of 30% hydrogen peroxide, after the solution is golden yellow and generated bubbles are gradually dissipated, adding 250ml of 37% concentrated hydrochloric acid, stirring uniformly, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.0, adding 300g of sodium bicarbonate into the solution, heating to 90 ℃ and stirring at constant temperature for 120min, cooling to 40 ℃, decompressing and distilling the obtained solution to 1/50 of the original volume under 40 ℃, continuously adding absolute ethyl alcohol until the appearing crystals are not increased, stopping adding absolute ethyl alcohol, layering, filtering, washing, and drying to remove the absolute ethyl alcohol and crystals in the solution to obtain the graphene.
Microscopic images of the graphene water-based dispersion at different magnifications as shown in fig. 1; from this figure, it can be seen that the graphene is dispersed more uniformly in water.
5.0g of the graphene, 3.0g of a surfactant (sodium pyrrolidone-based carboxylate: isodeca alcohol polyoxyethylene ether 1030=1:1 (w/w)) and 92.0g of water are taken, and then 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 dry, scaly, graphite powder with purity higher than 95% and mesh number of 500 meshes into the round bottom flask under stirring, cooling the graphite sulfuric acid mixed solution to 5 ℃, adding 75g of potassium permanganate powder under stirring, heating to 38 ℃, stirring for 3 hours, transferring the reaction solution into 2500ml of ice-water mixture, adding 180ml of 30% hydrogen peroxide, after the solution is golden yellow and the generated bubbles are gradually dissipated, adding 250ml of 37% concentrated hydrochloric acid, stirring uniformly, adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.5, adding 200g of ammonium carbonate into the solution, heating to 90 ℃ and stirring at constant temperature for 120min, cooling to 40 ℃, decompressing and distilling the obtained solution to 1/40 of the original volume under 40 ℃, continuously adding absolute ethyl alcohol until the generated crystals are not increased, stopping absolute ethyl alcohol addition, layering, filtering, washing, and drying to remove pure graphene obtained after ethanol and crystalline substances in the solution.
5.0g of the graphene, 3.4g of a surfactant (sodium cetyl sulfonate: polyoxyethylene sorbitan monopalmitate=0.8:1.2 (w/w)) and 91.6g of water are taken, and then uniformly dispersed at a high speed to obtain the graphene water-based dispersion.
Example 3
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round bottom flask, adding 20g of dry, scaly and graphite powder with purity higher than 95% and mesh number of 1200 meshes into the round bottom flask under stirring, cooling the graphite sulfuric acid mixed solution to 4 ℃, adding 70g of potassium permanganate powder under stirring, heating to 40 ℃, stirring for 2 hours, transferring the reaction solution into 2500ml of ice-water mixture, adding 140ml of 30% hydrogen peroxide, after the solution is golden yellow and generated bubbles are gradually dissipated, adding 250ml of 37% concentrated hydrochloric acid, stirring uniformly, then adding 3mol/L sodium hydroxide aqueous solution until the pH value of the solution is 9.0, adding 350g of potassium bicarbonate into the solution, heating to 80 ℃ and stirring for 180min at constant temperature, cooling to 40 ℃, decompressing and distilling the obtained solution to 1/25 of the original volume under 35 ℃, continuing adding absolute ethyl alcohol until the generated crystals are not increased, stopping absolute ethyl alcohol addition, layering, filtering, washing, and drying to remove the ethanol and crystalline substances in the solution to obtain graphene.
5.5g of the graphene, 4.0g of surfactant (alkanolamide succinic acid monoester disodium salt: amido surfactant TMA-1=0.9:1.1 (w/w)) and 90.5g of water are taken, and then uniformly dispersed 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 dry, scaly and graphite powder with purity higher than 95% and mesh number of 1200 meshes into the round bottom flask under stirring, cooling the graphite sulfuric acid mixed solution to 5 ℃, adding 76g of potassium permanganate powder under stirring, heating to 39 ℃, stirring for 3.5h, transferring the reaction solution into 2500ml of ice-water mixture, adding 220ml of 30% hydrogen peroxide, after the solution is golden yellow and generated bubbles are gradually dissipated, adding 250ml of 37% concentrated hydrochloric acid, stirring uniformly, then adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.5, adding 300g of sodium bicarbonate into the solution, heating to 85 ℃ and stirring at constant temperature for 150min, cooling to 40 ℃, decompressing and distilling the obtained solution to 1/35 of the original volume under 40 ℃, continuously adding absolute ethanol until the generated crystals are not increased, stopping absolute ethanol addition, layering, filtering, washing, and drying to remove ethanol and crystalline substances in the solution, thereby obtaining pure graphene.
Taking 5.5g of the graphene, 4.0g of surfactant (N-lauroyl sarcosine sodium: nonionic block water-based polyurethane surfactant=0.6:1.4 (w/w)) and 90.5g of water, and uniformly dispersing at a high speed to obtain the graphene water-based dispersion.
Example 5
Adding 500ml of 95-98% concentrated sulfuric acid into a 1000ml round bottom flask, adding 20g of dry, scaly, graphite powder with purity higher than 95% and mesh number of 800 meshes into the round bottom flask under stirring, cooling the graphite sulfuric acid mixed solution to 3 ℃, adding 80g of potassium permanganate powder under stirring, heating to 40 ℃, stirring for 3 hours, transferring the reaction solution into 2500ml of ice-water mixture, adding 200ml of 30% hydrogen peroxide, after the solution is golden yellow and generated bubbles are gradually dissipated, adding 250ml of 37% concentrated hydrochloric acid, stirring uniformly, then adding 2.5mol/L sodium hydroxide aqueous solution until the pH value of the solution is 8.8, adding 350g of potassium bicarbonate into the solution, heating to 85 ℃ and stirring at constant temperature for 150 minutes, cooling to 40 ℃, decompressing and distilling the obtained solution to 1/30 of the original volume under 40 ℃, continuously adding absolute ethyl alcohol until the generated crystals are not increased, stopping absolute ethyl alcohol addition, layering, filtering, washing, and drying to remove pure graphene obtained after ethanol and crystalline substances in the solution.
5.2g of the graphene, 3.8g of surfactant (sodium hexadecylsulfonate: oleamide=1.6:0.4 (w/w)) and 91.0g of water were taken, and after uniform dispersion at 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 foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all modifications or equivalent arrangements using the teachings of this invention, or direct or indirect application in other related arts, are included within the scope of this invention.
Claims (9)
1. The preparation method of the graphene is characterized by comprising the following steps of:
(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; the specific preparation process of the acidic multi-impurity graphene oxide dispersion liquid comprises the following steps: adding dry graphite powder into 95-98% concentrated sulfuric acid in a stirring state, continuously and slowly adding potassium permanganate powder in a temperature condition of 2-5 ℃ and in the stirring state, heating to 35-40 ℃, keeping the stirring state for 2-4 hours, transferring the obtained solution into an ice-water mixture of deionized water, adding hydrogen peroxide into a 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 an acidic multi-impurity graphene oxide dispersion;
(2) Adding carbonate into the multi-impurity graphene oxide dispersion liquid obtained in the step (1), and stirring for reaction to obtain multi-impurity graphene dispersion liquid;
(3) Concentrating the multi-impurity graphene dispersion liquid obtained in the step (2) by reduced pressure distillation, and then slowly adding a non-aqueous solvent into the multi-impurity graphene dispersion liquid until crystals are not increased any more, and stopping adding the non-aqueous solvent; adding a nonaqueous solvent into the concentrated multi-impurity graphene dispersion liquid to crystallize and separate out impurities, and forming an expansion effect by the crystallization of inorganic salts attached to and inserted between graphene layers to promote the peeling of graphene sheets;
(4) And (3) layering, filtering, washing with water, and drying to remove the crystals and the nonaqueous solvent in the mixed solution obtained in the step (3) to obtain the graphene.
2. The preparation method of the graphene according to claim 1, wherein the concentration of the hydrogen peroxide is more than or equal to 25%, and the concentration of the concentrated hydrochloric acid is more than or equal to 35%.
3. The preparation method of graphene according to claim 1, wherein the graphite powder is flake-shaped, has a purity of not less than 95%, a mesh number of 500-1200 meshes and a water content of less than 0.1%.
4. The preparation method of graphene according to claim 1, wherein the alkaline solution is an aqueous solution with a 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.
5. The preparation method of graphene according to claim 1, wherein the reaction temperature in the step (2) is 60-95 ℃ and the reaction time is 120-180 min.
6. The method for preparing graphene according to claim 1, wherein the carbonate is one of ammonium carbonate, potassium bicarbonate, sodium bicarbonate and ammonium bicarbonate.
7. The method for preparing graphene according to claim 1, wherein in the step (3), the reduced pressure distillation is performed at a temperature of 35-45 ℃.
8. Graphene, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. The graphene water-based dispersion is characterized in that the graphene water-based dispersion is obtained by uniformly dispersing graphene and a surfactant in water at a high speed.
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| JP2011032156A (en) * | 2009-07-06 | 2011-02-17 | Kaneka Corp | Method for manufacturing graphene or thin film graphite |
| CN105776192A (en) * | 2016-02-26 | 2016-07-20 | 成都新柯力化工科技有限公司 | Method for continuously preparing graphene nanoplatelets by means of grinding stripping |
| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
| CN112960668A (en) * | 2021-01-11 | 2021-06-15 | 山东理工大学 | Method for preparing graphene powder by water-phase enhanced stripping method |
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| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
| CN105776192A (en) * | 2016-02-26 | 2016-07-20 | 成都新柯力化工科技有限公司 | Method for continuously preparing graphene nanoplatelets by means of grinding stripping |
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