CN113247888B - Graphene composite material and preparation method thereof - Google Patents
Graphene composite material and preparation method thereof Download PDFInfo
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- CN113247888B CN113247888B CN202110461365.4A CN202110461365A CN113247888B CN 113247888 B CN113247888 B CN 113247888B CN 202110461365 A CN202110461365 A CN 202110461365A CN 113247888 B CN113247888 B CN 113247888B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 71
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 34
- 239000010439 graphite Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229940117975 chromium trioxide Drugs 0.000 claims abstract description 22
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 159000000009 barium salts Chemical class 0.000 claims abstract description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims abstract description 8
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 208000004761 Supernumerary Tooth Diseases 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 22
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 20
- -1 barium chromate-barium sulfate Chemical compound 0.000 claims description 19
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 14
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 6
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 210000004357 third molar Anatomy 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C01B32/19—Preparation by exfoliation
-
- 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 application relates to the field of functional materials, and provides a preparation method of a graphene composite material, which comprises the following steps: dissolving a first mole amount of chromium trioxide in a second mole amount of water to form a chromic acid solution, slowly dropwise adding a third mole amount of concentrated sulfuric acid into the chromic acid solution in a stirring state, and stirring until the third mole amount of concentrated sulfuric acid is uniformly mixed to form a mixed solution; adding a fourth molar amount of expanded graphite to the mixed solution, forming a mixed system of intercalated graphite composition under first agitation conditions; treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain graphene mixed solution; under the second stirring condition, adding basic barium salt of barium into the graphene mixed solution to form a suspension, and slowly adjusting the pH of the suspension to be near neutral; spray drying the suspension to obtain a powdery graphene composite material; or distilling and concentrating the suspension to obtain concentrated slurry of the dispersed graphene composite material, so as to improve the dispersibility of the graphene.
Description
Technical Field
The application relates to the technical field of functional materials, in particular to a graphene composite material and a preparation method thereof.
Background
Graphene (Graphene) is a hexagonal two-dimensional crystal with a honeycomb structure, which is constructed by carbon atoms in an sp2 hybridized form, has excellent mechanical, optical and electrical properties, and has a very stable structure. To date, researchers have not found that graphene has a lack of carbon atoms, the connection between carbon atoms is very tough, the force between carbon atoms is 100 times stronger than diamond, and if the packaging bag is made of graphene, it will be able to withstand about two tons of items. The single-layer graphene is almost completely transparent, and each layer of graphene only absorbs 2.3% of light, but is extremely dense, impermeable to water and gas, and cannot be penetrated by helium with the smallest atomic size. The single-layer graphene has good conductivity, the movement speed of electrons reaches 1/300 of the speed of light, and the conductivity is superior to that of the traditional conductive material. The graphene surface can adsorb and desorb various atoms and molecules, so that the graphene has the capability of resisting strong acid and strong alkali. The excellent performance of the graphene enables the graphene to have great potential application value in the fields of gas sensors, optoelectronic devices, chemical energy sources (solar batteries and lithium ion batteries), coatings and the like.
However, in practical application, the graphene sheets are easy to aggregate, the performance of the graphene is affected, the graphene is generally required to be dispersed in an organic solvent or an aqueous solution containing a surfactant to form a graphene dispersion, solvent molecules or surfactant molecules are adsorbed on the surface of the graphene, and monolayer dispersion of the graphene is realized by means of intermolecular forces or electrostatic repulsive forces of the solvent molecules or the surfactant molecules, but the dispersion degree of the graphene dispersion (liquid) is low, the dispersion state is unstable, the concentration is low, and the wide development of the graphene is still limited.
Disclosure of Invention
The application provides a graphene composite material and a preparation method thereof, and aims to solve the technical problems of low dispersity, unstable dispersion state and low concentration of the existing graphene dispersion (liquid).
The application provides a preparation method of a graphene composite material, which comprises the following steps:
dissolving a first mole amount of chromium trioxide in a second mole amount of water to form a chromic acid solution, slowly dropwise adding a third mole amount of concentrated sulfuric acid into the chromic acid solution in a stirring state, and stirring until the third mole amount of concentrated sulfuric acid is uniformly mixed to form a mixed solution;
adding a fourth molar amount of expanded graphite to the mixed solution, forming a mixed system of intercalated graphite composition under first agitation conditions;
treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain graphene mixed solution;
under the second stirring condition, adding basic barium salt of barium into the graphene mixed solution to form a suspension, and slowly adjusting the pH of the suspension to be near neutral;
spray drying the suspension to obtain a powdery graphene composite material; or distilling and concentrating the suspension to obtain concentrated slurry of the dispersed graphene composite material.
Preferably, the fourth molar amount: first molar amount: third molar amount: the ratio of the second molar amount is 10 (1-10): 1-5): 45-70.
Preferably, the first stirring condition comprises a pressure range of 4MPa to 8MPa, a stirring speed of 0.2m/s to 1m/s and a stirring reaction time of 0.5h to 24h.
Preferably, the first stirring condition comprises a pressure range of 6MPa to 8MPa, a stirring speed of 0.5m/s to 1m/s and a stirring reaction time of 12h.
Preferably, the specified stripping conditions comprise a stripping high-pressure range of 150-200 MPa, a stripping temperature range of 10-80 ℃ and a number of high-pressure homogenizing stripping channels of 2-5 channels.
Preferably, the specified stripping conditions comprise a stripping high-pressure range of 180-200 MPa, a stripping temperature range of 20-60 ℃ and 3-4 high-pressure homogenizing stripping channels.
Preferably, the basic barium salt comprises one or more of barium hydroxide, barium carbonate and basic barium carbonate.
Preferably, the drying temperature of the spray drying is 50-200 ℃, and the temperature of the distillation concentration is 50-120 ℃.
The application also provides a graphene composite material, which is prepared by the preparation method of the graphene composite material, wherein the graphene composite material comprises graphene and barium chromate-barium sulfate, and the ratio range of the amount of the graphene to the amount of the barium chromate-barium sulfate substance comprises 1:0.2-1:1.5.
Preferably, the particle size of the barium chromate-barium sulfate is 5nm to 1mm.
According to the method, the barium chromate-barium sulfate is introduced into the graphene powder, so that secondary agglomeration of the graphene material is effectively prevented, the powder of the graphene composite material is easier to disperse in slurry with larger density, the dispersibility of the graphene powder material is improved, the application universality of the graphene powder material is further improved, the method can be widely applied to various coating materials, rubber materials, plates and other compound materials, and the original manufacturing process is not required to be changed while the dispersibility is improved.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of a graphene composite material in an embodiment of the present application.
Detailed Description
The preparation method of the graphene composite material in the application is specifically described by combining the following examples, and the synthesis steps are as follows:
a) Dissolving a first mole amount of chromium trioxide in a second mole amount of water to form a chromic acid solution, slowly dropwise adding a third mole amount of concentrated sulfuric acid into the chromic acid solution in a stirring state, and stirring until the third mole amount of concentrated sulfuric acid is uniformly mixed to form a mixed solution;
b) Adding a fourth molar amount of expanded graphite to the mixed solution to form a mixed system of intercalated graphite composition under the first stirring condition;
c) Treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain graphene mixed solution;
d) Under the second stirring condition, forming a suspension by adding basic barium salt into the graphene mixed solution, and slowly adjusting the pH of the suspension to be near neutral;
e) Spray drying the suspension to obtain a powdery graphene composite material; or distilling and concentrating the suspension to obtain concentrated slurry of dispersed graphene composite material, wherein the graphene composite material is barium chromate-barium sulfate composite graphene, and the morphology is shown in figure 1.
According to the method, the barium chromate-barium sulfate is introduced into the graphene powder, so that secondary agglomeration of the graphene material is effectively prevented, the powder of the graphene composite material is easier to disperse in slurry with larger density, the dispersibility of the graphene powder material is improved, the application universality of the graphene powder material is further improved, the method can be widely applied to various coating materials, rubber materials, plates and other compound materials, and the original manufacturing process is not required to be changed while the dispersibility is improved.
The fourth molar amount: first molar amount: third molar amount: the ratio of the second molar amount is 10 (1-10): 1-5): 45-70. The particle size of the expanded graphite is 5nm to 100. Mu.m, preferably 10nm to 40. Mu.m, and the carbon content of the graphite is higher than 80%, preferably 95% or more; the purity of the chromium trioxide is more than 95%, preferably more than 99%; the concentration of the concentrated sulfuric acid is 90% or more, preferably 98%; the water is deionized water or secondary distilled water so as to improve the purity of the graphene composite material.
The first stirring condition comprises the pressure range of 4MPa to 8MPa, preferably 6MPa to 8MPa, and the pressurizing mode is the air pressurizing of a common air compressor; the stirring speed is 0.2 m/s-1 m/s, preferably 0.5 m/s-1 m/s; the stirring reaction time is 0.5h to 24h, and the comprehensive production efficiency and quality are preferably 12h, so that the uniformity of stirring and mixing is provided, and the uniformity of barium chromate-barium sulfate composite graphene is improved.
The specified stripping conditions comprise that the stripping high-pressure range is 150-200 MPa, and 180-200 MPa is preferable for improving the single-channel stripping effect; the stripping temperature ranges from 10 ℃ to 80 ℃ and is preferably 20 ℃ to 60 ℃ for improving the single-path stripping effect; the number of the high-pressure homogenizing stripping channels is 2-5, and 3-4 high-pressure homogenizing stripping is preferably performed on the premise of ensuring the stripping effect so as to improve the production efficiency. The number of the high-pressure homogenizing stripping channels refers to the number of times of high-pressure stripping when the expanded graphite enters the high-pressure bin, and the expanded graphite enters and flows out of the high-pressure bin for each single-channel stripping process, and is stripped into oligolayer graphite or even single-layer graphite, preferably less than 5 layers through multi-channel high-pressure homogenizing stripping.
The basic barium salt includes, but is not limited to, barium hydroxide, barium carbonate, basic barium carbonate, etc., and barium hydroxide or barium carbonate is preferred for improving the purity of the graphene composite material. The PH of the suspension is slowly adjusted to be in a neutral range, namely the PH is 6.5-7.5, preferably 6.8-7.2, and the reaction time for adjusting the PH value is 2-24 hours, preferably 1-2 hours, so that the sufficient and uniform precipitation of barium salt is ensured, and the uniform dispersion degree of barium chromate-barium sulfate in the graphene composite material is improved.
The drying temperature of the suspension for spray drying is 50-200 ℃, preferably 80-150 ℃. The temperature range of distillation concentration of the suspension is 50-120 ℃, preferably 80-105 ℃. The spray drying device and the distillation concentration device are both provided with condensing devices, and are used for recycling water in the recycling process.
The graphene composite material is simple in manufacturing equipment and extremely easy to realize industrial production, the technological process sequentially comprises intercalation, stripping, neutralization (granulation), drying or concentration, and the corresponding input equipment comprises a pressure tank with stirring, a high-pressure homogenizer, a stirring kettle, a spray dryer (with a condenser) or a concentrating device (with a condenser). When the finally required graphene composite material is dry powder, selecting a spray dryer; when the final desired graphene composite material is a concentrated slurry, a concentrating device is selected. And D, selecting a stirring kettle in the step D to be heatable when selecting a concentration device, directly heating, distilling and concentrating under stirring conditions, and directly introducing the gas volatilized by subsequent distillation into a condenser through a hose for cooling and recycling.
In the whole process, no waste gas is generated, all reactants are generated into solid and water, the environment is protected, no pollution is caused, no waste gas, waste water and waste solid three wastes are discharged, the pollution chromium trioxide and sulfuric acid can be generated into insoluble barium chromate and barium sulfate solid particles through neutralization/reduction, and the solid particles do not need to be cleaned and discharged as a part of the composite material, so that the zero emission of heavy metals and acidic substances is realized; in the drying process, the water recovered by cooling can be reused in the preparation of the next batch without discharge, and the whole process realizes the integral zero discharge and belongs to a completely environment-friendly product.
Example 1:
the raw materials are as follows: 10mol of expanded graphite, 1mol of chromium trioxide, 1mol of sulfuric acid, 50mol of water and a proper amount of barium hydroxide.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 8MPa after uniformly stirring again, wherein the stirring speed is 0.2m/s, and stirring for 0.5h. And stripping 2 times by using a temperature-controllable high-pressure homogenizing and dispersing machine under the stripping condition of the temperature of 10 ℃ and the pressure of 150MPa to generate graphene dispersion liquid. Slowly adding barium hydroxide into graphene dispersion liquid at the stirring speed of 0.5m/s, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, fine-tuning to 6.8, performing spray drying or distillation concentration, drying at 50 ℃ and collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 50 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 1 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate at 50 μm, and the graphene composite material obtained in the example 1 is extremely easy to disperse and has small bulk density.
Example 2:
the raw materials are as follows: 10mol of expanded graphite, 2mol of chromium trioxide, 1mol of sulfuric acid, 55mol of water and a proper amount of barium hydroxide.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 6MPa after uniformly stirring again, and stirring for 2h at a linear speed of 0.4 m/s. And (3) stripping 5 times under the stripping condition of the temperature of 20 ℃ and the pressure of 180MPa by using a temperature-controllable high-pressure homogenizing and dispersing machine to generate graphene dispersion liquid. Slowly adding barium hydroxide into graphene dispersion liquid at a stirring speed of 8m/s, adjusting the pH value to 7.2, reacting for 12 hours, detecting the pH value again, fine-tuning to 7.2, performing spray drying or distillation concentration, drying at 80 ℃ and collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 80 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 2 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate at 700 mu m, and the graphene composite material obtained in the example 2 is extremely easy to disperse and has small bulk density.
Example 3:
the raw materials are as follows: 10mol of expanded graphite, 5mol of chromium trioxide, 2mol of sulfuric acid, 70mol of water and a proper amount of barium hydroxide.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 7MPa after uniformly stirring again, stirring at a linear speed of 0.4m/s, and stirring for reacting for 12h. And (3) stripping the graphene by using a temperature-controllable high-pressure homogenizing and dispersing machine under stripping conditions of temperature 80 ℃ and pressure of 200MPa to generate graphene dispersion liquid. Slowly adding barium hydroxide into graphene dispersion liquid at the stirring speed of 9m/s at the linear speed, adjusting the pH value to 7.0, detecting the pH value again after reacting for 1h, fine-tuning to 7.0, performing spray drying or distillation concentration, collecting powder after drying at 100 ℃ to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 100 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 3 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate, 3 mu m, and the graphene composite material obtained in the embodiment 3 is extremely easy to disperse and has small bulk density.
Example 4:
the raw materials are as follows: 10mol of expanded graphite, 3mol of chromium trioxide, 5mol of sulfuric acid, 45mol of water and a proper amount of barium hydroxide.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 5MPa after uniformly stirring again, and stirring for 2h at a linear speed of 0.6 m/s. And (3) stripping the graphene by using a temperature-controllable high-pressure homogenizing and dispersing machine under stripping conditions of 60 ℃ and 190MPa to generate graphene dispersion liquid. Slowly adding barium hydroxide into graphene dispersion liquid at the stirring speed of 10m/s at the linear speed, adjusting the pH value to 7.0, detecting the pH value again after reacting for 1h, fine-tuning to 7.0, performing spray drying or distillation concentration, collecting powder after drying at 120 ℃ to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 120 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 4 50 30 mu m, graphene is well adhered to solid particles of barium chromate-barium sulfate, and the solid particles are solidThe graphene composite material obtained in example 4 is extremely easy to disperse and has a small bulk density.
Example 5:
the raw materials are as follows: 10mol of expanded graphite, 10mol of chromium trioxide, 5mol of sulfuric acid, 70mol of water and a proper amount of barium hydroxide.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 8MPa after uniformly stirring again, stirring at a linear speed of 1m/s, and stirring for reaction for 24h. And (3) stripping 5 times under the stripping condition of the temperature of 80 ℃ and the pressure of 200MPa by using a temperature-controllable high-pressure homogenizing and dispersing machine to generate graphene dispersion liquid. Slowly adding barium hydroxide into graphene dispersion liquid at the stirring speed of 10m/s at the linear speed, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, fine-tuning to 6.8, performing spray drying or distillation concentration, drying at 150 ℃, collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 110 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 5 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate, the graphene composite material obtained in the example 5 is extremely easy to disperse, and the bulk density is small.
Example 6:
the raw materials are as follows: 10mol of expanded graphite, 8mol of chromium trioxide, 5mol of sulfuric acid, 70mol of water and a proper amount of barium carbonate.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 8MPa after uniformly stirring again, and stirring for reaction for 24h at a linear speed of 0.5 m/s. And (3) stripping 5 times under the stripping condition of the temperature of 80 ℃ and the pressure of 200MPa by using a temperature-controllable high-pressure homogenizing and dispersing machine to generate graphene dispersion liquid. Then slowly adding barium carbonate into graphene dispersion liquid at the stirring speed of 10m/s at the linear speed, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, fine-tuning to 6.8, performing spray drying or distillation concentration, drying at 80 ℃ and collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or concentrating by distillation at 105 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 6 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate, 20 mu m, and the graphene composite material obtained in the example 6 is extremely easy to disperse and has small bulk density.
Example 7:
the raw materials are as follows: 10mol of expanded graphite, 2mol of chromium trioxide, 5mol of sulfuric acid, 50mol of water and a proper amount of barium carbonate.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 4MPa after uniformly stirring again, stirring at a linear speed of 1m/s, and stirring for reaction for 24h. And (3) stripping 4 times by using a temperature-controllable high-pressure homogenizing and dispersing machine under the stripping condition of the temperature of 70 ℃ and the pressure of 200MPa to generate graphene dispersion liquid. Then slowly adding barium carbonate into graphene dispersion liquid at the stirring speed of 10m/s at the linear speed, adjusting the pH value to 6.5, reacting for 2 hours, detecting the pH value again, fine-tuning to 6.5, then performing spray drying or distillation concentration, drying at 180 ℃ and collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 120 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 7 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate with the thickness of 100 mu m, and the graphene composite material obtained in the example 7 is extremely easy to disperse and has small bulk density.
Example 8:
the raw materials are as follows: 10mol of expanded graphite, 7mol of chromium trioxide, 3mol of sulfuric acid, 50mol of water and a proper amount of basic barium carbonate.
The preparation method comprises the following steps: dissolving chromium trioxide in water, slowly adding concentrated sulfuric acid dropwise under stirring, adding expanded graphite after completely and uniformly mixing, pressurizing with air at 7MPa after uniformly stirring again, stirring at a linear speed of 0.2m/s, and stirring for reacting for 12h. And stripping 2 times by using a temperature-controllable high-pressure homogenizing and dispersing machine under the stripping condition of the temperature of 60 ℃ and the pressure of 180MPa to generate graphene dispersion liquid. Slowly adding basic barium carbonate into graphene dispersion liquid at the stirring speed of 1m/s, adjusting the pH value to 7.5, reacting for 24 hours, detecting the pH value again, fine-tuning to 7.5, performing spray drying or distillation concentration, drying at 200 ℃ and collecting powder to obtain graphene composite material, and recovering cooling fractional moisture; or distilling and concentrating at 120 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite Material obtained in example 8 50 The graphene is well adhered to solid particles of barium chromate-barium sulfate at 1000 mu m, and the graphene composite material obtained in the example 8 is extremely easy to disperse and has small bulk density.
The above examples of the present application are merely examples for clearly illustrating the present application and are not limiting of the embodiments of the present application. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modifications, equivalent substitutions, improvements, etc. that fall within the spirit and principles of the present application are intended to be included within the scope of the present application.
Claims (8)
1. The preparation method of the graphene composite material is characterized by comprising the following steps of:
dissolving a first mole amount of chromium trioxide in a second mole amount of water to form a chromic acid solution, slowly dropwise adding a third mole amount of concentrated sulfuric acid into the chromic acid solution in a stirring state, and stirring until the third mole amount of concentrated sulfuric acid is uniformly mixed to form a mixed solution;
adding a fourth molar amount of expanded graphite to the mixed solution, under first agitation conditions, to form a mixed system of intercalated graphite compositions, the fourth molar amount: first molar amount: third molar amount: the ratio of the second molar quantity is 10 (1-10): 1-5): 45-70, and the pressure of the first stirring condition is 4-8 MPa;
treating the mixed system under specified stripping conditions, and carrying out high-pressure homogenization stripping on the intercalated graphite composition to obtain graphene mixed solution, wherein the specified stripping conditions comprise a stripping high-pressure range of 150-200 MPa, a stripping temperature range of 10-80 ℃ and a number of high-pressure homogenization stripping channels of 2-5 channels;
adding basic barium salt into the graphene mixed solution under a second stirring condition to form a suspension, and slowly adjusting the pH of the suspension to be near neutral, wherein the pH is 6.5-7.5;
spray drying the suspension to obtain a powdery graphene composite material; or distilling and concentrating the suspension to obtain concentrated slurry of the dispersed graphene composite material.
2. The method for preparing a graphene composite material according to claim 1, wherein the stirring speed under the first stirring condition is 0.2-1 m/s, and the stirring reaction time is 0.5-24 h.
3. The method for preparing a graphene composite material according to claim 2, wherein the first stirring condition includes a pressure range of 6MPa to 8MPa, a stirring speed of 0.5m/s to 1m/s, and a stirring reaction time of 12h.
4. The method for preparing the graphene composite material according to claim 1, wherein the specified peeling conditions comprise peeling high pressure ranging from 180mpa to 200mpa, peeling temperature ranging from 20 ℃ to 60 ℃ and the number of high-pressure homogenizing peeling channels ranging from 3 to 4.
5. The method of preparing a graphene composite material according to claim 1, wherein the basic barium salt comprises one or more of barium hydroxide, barium carbonate, and basic barium carbonate.
6. The method for preparing a graphene composite material according to claim 1, wherein the drying temperature of the spray drying is 50-200 ℃, and the temperature of the distillation concentration is 50-120 ℃.
7. A graphene composite material, characterized in that the graphene composite material is prepared by the preparation method of the graphene composite material according to any one of claims 1-6, wherein the graphene composite material comprises graphene and barium chromate-barium sulfate, and the ratio of the amount of the graphene to the amount of the barium chromate-barium sulfate is in the range of 1:0.2-1:1.5.
8. The graphene composite material according to claim 7, wherein the particle size of barium chromate-barium sulfate is 3um to 1mm.
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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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| CN108002376A (en) * | 2017-11-02 | 2018-05-08 | 广东华材实业股份有限公司 | A kind of high stable graphene dispersion body and preparation method thereof |
| CN108054376A (en) * | 2017-12-26 | 2018-05-18 | 深圳先进技术研究院 | Seleno composite material is used as application of the positive electrode active materials in barium ions battery, barium ions battery and preparation method thereof |
| CN109021633A (en) * | 2018-06-21 | 2018-12-18 | 深圳陶金材料科技有限公司 | A kind of graphene-based high-temperature coatings and preparation method thereof |
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| WO2017128929A1 (en) * | 2016-01-27 | 2017-08-03 | 复旦大学 | Method for preparing graphene dispersion and article thereof |
| CN107416811A (en) * | 2017-06-21 | 2017-12-01 | 山东欧铂新材料有限公司 | A kind of preparation method of high conductivity graphene |
| CN108002376A (en) * | 2017-11-02 | 2018-05-08 | 广东华材实业股份有限公司 | A kind of high stable graphene dispersion body and preparation method thereof |
| CN108054376A (en) * | 2017-12-26 | 2018-05-18 | 深圳先进技术研究院 | Seleno composite material is used as application of the positive electrode active materials in barium ions battery, barium ions battery and preparation method thereof |
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