CN113247888A - Graphene composite material and preparation method thereof - Google Patents
Graphene composite material and preparation method thereof Download PDFInfo
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- CN113247888A CN113247888A CN202110461365.4A CN202110461365A CN113247888A CN 113247888 A CN113247888 A CN 113247888A CN 202110461365 A CN202110461365 A CN 202110461365A CN 113247888 A CN113247888 A CN 113247888A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 75
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 159000000009 barium salts Chemical class 0.000 claims abstract description 9
- 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
- 239000000243 solution Substances 0.000 claims abstract description 8
- 208000004761 Supernumerary Tooth Diseases 0.000 claims abstract description 7
- 210000004357 third molar Anatomy 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 25
- 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
- 238000001035 drying Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 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
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- 238000005054 agglomeration Methods 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 238000007599 discharging Methods 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
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 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
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- 239000002351 wastewater Substances 0.000 description 1
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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
- 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 chromium trioxide with a first molar amount in water with a second molar amount to form a chromic acid solution, slowly adding concentrated sulfuric acid with a third molar amount dropwise into the chromic acid solution while stirring, and stirring until the mixture is uniformly mixed to form a mixed solution; adding expanded graphite with a fourth molar weight into the mixed solution, and forming a mixed system of the intercalated graphite composition under the first stirring condition; treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain a graphene mixed solution; under the second stirring condition, forming a suspension by adding alkali barium salt in the graphene mixed solution, and slowly adjusting the pH near-neutral range of the suspension by adding basic salt of barium; carrying out spray drying on 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 honeycomb-structured two-dimensional crystal constructed by carbon atoms in an sp2 hybridization manner, has excellent mechanical, optical and electrical properties, and is very stable in structure. To date, researchers have not found that graphene is lacking in carbon atoms, the bonds between carbon atoms are very strong, the forces between carbon atoms are harder than diamond and 100 times stronger than steel, and graphene can withstand about two tons of weight if used in a package. Single-layer graphene is almost completely transparent, each layer of graphene absorbs only 2.3% of light, but is extremely dense, impermeable to water, impermeable to air, and impermeable to helium gas even of 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 has the capability of resisting strong acid and strong alkali because the surface of the graphene can adsorb and desorb various atoms and molecules. Due to the excellent performance of the graphene, the graphene has great potential application value in the fields of gas sensors, optoelectronic devices, chemical energy sources (solar cells and lithium ion batteries), coatings and the like.
However, in practical applications, graphene sheets are easily aggregated to affect the performance of graphene, and graphene is generally required to be dispersed in an organic solvent or an aqueous solution containing a surfactant to form a graphene dispersion, so that solvent molecules or surfactant molecules are adsorbed on the surface of graphene, and the single-layer dispersion of graphene is realized by virtue of intermolecular forces or electrostatic repulsive forces of the solvent molecules or surfactant molecules, but the wide development of graphene is still limited due to the low dispersion degree, unstable dispersion state and low concentration of the graphene dispersion (liquid).
Disclosure of Invention
The application provides a graphene composite material and a preparation method thereof, aiming at solving the technical problems of low dispersion degree, 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 chromium trioxide with a first molar amount in water with a second molar amount to form a chromic acid solution, slowly adding concentrated sulfuric acid with a third molar amount dropwise into the chromic acid solution while stirring, and stirring until the mixture is uniformly mixed to form a mixed solution;
adding a fourth molar amount of expanded graphite to the mixed solution to form a mixed system of intercalated graphite compositions under the first stirring condition;
treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain a graphene mixed solution;
under a second stirring condition, forming a suspension by adding alkali barium salt in the graphene mixed solution, and slowly adjusting the pH value of the suspension to be close to a neutral range by adding basic salt of barium;
carrying out spray drying on 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) to 1-5 to 45-70.
Preferably, the first stirring condition comprises a pressure intensity range of 4 MPa-8 MPa, a stirring speed of 0.2 m/s-1 m/s and a stirring reaction time of 0.5 h-24 h.
Preferably, the first stirring condition comprises that the pressure intensity is 6 MPa-8 MPa, the stirring speed is 0.5 m/s-1 m/s, and the stirring reaction time is 12 h.
Preferably, the specified stripping conditions comprise that the stripping high-pressure range is 150 MPa-200 MPa, the stripping temperature range is 10 ℃ -80 ℃, and the number of high-pressure homogeneous stripping channels is 2-5.
Preferably, the specified stripping conditions comprise that the stripping high-pressure range is 180 MPa-200 MPa, the stripping temperature range is 20 ℃ -60 ℃, and the number of high-pressure homogeneous stripping channels is 3-4.
Preferably, the basic barium salt comprises one or more of barium hydroxide, barium carbonate and basic barium carbonate.
Preferably, the drying temperature range of the spray drying is 50-200 ℃, and the temperature range of the distillation concentration is 50-120 ℃.
The application also provides a graphene composite material prepared by the preparation method of the graphene composite material, 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 substance is 1: 0.2-1: 1.5.
Preferably, the particle size of the barium chromate-barium sulfate is 5nm to 1 mm.
According to the preparation method, the barium chromate-barium sulfate is introduced into the graphene powder, so that secondary agglomeration of the graphene material is effectively hindered, the powder of the graphene composite material is easily dispersed in slurry at a high density, the dispersibility of the graphene powder material is improved, the applicability of the graphene powder material is further improved, the preparation method can be widely applied to various coating materials, rubber materials, plates and other compound materials, and the original preparation 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 according to an embodiment of the present disclosure.
Detailed Description
The following examples are combined to specifically illustrate the preparation method of the graphene composite material in the present application, and the synthesis steps are as follows:
A) dissolving chromium trioxide with a first molar amount in water with a second molar amount to form a chromic acid solution, slowly adding concentrated sulfuric acid with a third molar amount dropwise into the chromic acid solution while stirring, and stirring until the mixture is uniformly mixed to form a mixed solution;
B) adding expanded graphite with a fourth molar weight into the mixed solution, and forming a mixed system of the 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 a graphene mixed solution;
D) under a second stirring condition, basic barium salt in the graphene mixed solution forms a suspension, and the basic barium salt is added to slowly adjust the pH of the suspension to be close to a neutral range;
E) carrying out spray drying on the mixed suspension to obtain a powdery graphene composite material; or distilling and concentrating the suspension to obtain a concentrated slurry of a 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 preparation method, the barium chromate-barium sulfate is introduced into the graphene powder, so that secondary agglomeration of the graphene material is effectively hindered, the powder of the graphene composite material is easily dispersed in slurry at a high density, the dispersibility of the graphene powder material is improved, the applicability of the graphene powder material is further improved, the preparation method can be widely applied to various coating materials, rubber materials, plates and other compound materials, and the original preparation 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) to 1-5 to 45-70. The particle size range of the expanded graphite is 5 nm-100 mu m, preferably 10 nm-40 mu m, and the carbon content of the graphite is higher than 80%, preferably more than 95%; the purity of the chromium trioxide is more than 95%, preferably more than 99%; the concentration of the concentrated sulfuric acid is more than 90%, 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 a pressure intensity range of 4 MPa-8 MPa, preferably 6 MPa-8 MPa, and the pressurizing mode is air pressurization by 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 stirring and mixing uniformity is provided, and the uniformity of the barium chromate-barium sulfate composite graphene is improved.
The specified stripping conditions comprise that the stripping high-pressure range is 150 MPa-200 MPa, and 180 MPa-200 MPa is preferred for improving the single-pass stripping effect; the stripping temperature range is 10-80 ℃, and the preferred temperature is 20-60 ℃ for improving the single-pass stripping effect; the number of the high-pressure homogenizing stripping channels is 2-5, and 3-4 high-pressure homogenizing stripping channels are preferably selected on the premise of ensuring the stripping effect, so that the production efficiency is improved. The number of the high-pressure homogeneous stripping channels refers to the number of times of entering the high-pressure bin for high-pressure stripping, entering and exiting the high-pressure bin is a single-channel stripping process, and the expanded graphite is stripped into few layers of graphite or even single-layer graphite through multiple high-pressure homogeneous stripping, preferably less than 5 layers.
The basic barium salt includes, but is not limited to, barium hydroxide, barium carbonate, basic barium carbonate, and the like, and barium hydroxide or barium carbonate is preferred in order to improve the purity of the graphene composite material. And slowly adjusting the pH of the suspension to be in a neutral range, namely the pH is 6.5-7.5, preferably 6.8-7.2, and adjusting the pH value for 2-24 hours, preferably 1-2 hours, so as to ensure sufficient and uniform precipitation of barium salt and improve the uniform dispersion degree of barium chromate-barium sulfate in the graphene composite material.
The drying temperature range of the spray drying of the suspension is 50-200 ℃, and the preferred temperature range is 80-150 ℃. The temperature range of the distillation concentration of the suspension is 50-120 ℃, and the preferred temperature range is 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 process.
The preparation equipment of the graphene composite material is simple, industrial production is easy to realize, the process flow comprises intercalation, stripping, neutralization (granulation), drying or concentration in sequence, and the correspondingly-added equipment comprises a pressure tank with stirring, a high-pressure homogenizer, a stirring kettle, a spray dryer (with a condenser) or a concentration device (with a condenser). When the finally required graphene composite material is dry powder, a spray dryer is selected; when the finally required graphene composite material is concentrated slurry, a concentration device is selected. When the concentration device is selected, the stirring kettle in the step D can be selected to be heatable, the heating, the distillation and the concentration can be directly carried out under the stirring condition, and the subsequent gas volatilized by the distillation is directly connected 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 are discharged, polluted chromium trioxide and sulfuric acid are generated into insoluble barium chromate and barium sulfate solid particles through neutralization/reduction, and the solid particles are used as one part of the composite material and do not need to be cleaned and discharged, so that zero discharge of heavy metal and acidic substances is realized; in the drying process, the cooled and recovered water can be reused in the next batch of preparation without discharging, and the whole process realizes zero discharge on the whole, and belongs to a completely environment-friendly product.
Example 1:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 8MPa at a stirring speed of 0.2m/s, and stirring for reacting for 0.5 h. Stripping for 2 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of 10 ℃ and 150MPa to generate the graphene dispersion liquid. Then slowly adding barium hydroxide into the graphene dispersion liquid at a stirring speed of 0.5m/s, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, finely adjusting to 6.8, then performing spray drying or distillation concentration, drying at 50 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 150The thickness is 50 μm, graphene is well adhered to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 1 is very easy to disperse and has a small bulk density.
Example 2:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 6MPa at the stirring speed of 0.4m/s, and stirring for reacting for 2 h. Stripping for 5 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of the temperature of 20 ℃ and the pressure of 180MPa to generate the graphene dispersion liquid. Then slowly adding barium hydroxide into the 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, finely adjusting to 7.2, then performing spray drying or distillation concentration, drying at 80 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 250700 μm, the graphene is well adhered to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 2 is very easy to disperse and has a small bulk density.
Example 3:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 7MPa at the stirring speed of 0.4m/s, and stirring for reaction for 12 h. Stripping for 3 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of the temperature of 80 ℃ and the pressure of 200MPa to generate the graphene dispersion liquid. Then slowly adding barium hydroxide into the graphene dispersion liquid at a stirring speed of 9m/s, adjusting the pH value to 7.0, reacting for 1h, detecting the pH value again, finely adjusting to 7.0, then performing spray drying or distillation concentration, drying at 100 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 350The particle size is 3 μm, graphene is well attached to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 3 is very easy to disperse and has a low bulk density.
Example 4:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 5MPa at a stirring speed of 0.6m/s, and stirring for reacting for 2 h. Stripping for 3 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of 60 ℃ and 190MPa to generate the graphene dispersion liquid. Then slowly adding barium hydroxide into the graphene dispersion liquid at a stirring speed of 10m/s at a linear speed, adjusting the pH value to 7.0, reacting for 1h, detecting the pH value again, finely adjusting to 7.0, then performing spray drying or distillation concentration, drying at 120 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 450The thickness is 30 μm, graphene is well adhered to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 4 is very easy to disperse and has a small bulk density.
Example 5:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 8MPa, stirring at a linear speed of 1m/s, and reacting for 24 h. Stripping for 5 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of the temperature of 80 ℃ and the pressure of 200MPa to generate the graphene dispersion liquid. Then slowly adding barium hydroxide into the graphene dispersion liquid at a stirring speed of 10m/s at a linear speed, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, finely adjusting to 6.8, then performing spray drying or distillation concentration, drying at 150 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 550The thickness is 10 μm, graphene is well adhered to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 5 is very easy to disperse and has a small bulk density.
Example 6:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 8MPa, stirring at a linear speed of 0.5m/s, and stirring for reacting for 24 h. Stripping for 5 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of the temperature of 80 ℃ and the pressure of 200MPa to generate the graphene dispersion liquid. Then slowly adding barium carbonate into the graphene dispersion liquid at a stirring speed of 10m/s, adjusting the pH value to 6.8, reacting for 2 hours, detecting the pH value again, finely adjusting to 6.8, then performing spray drying or distillation concentration, drying at 80 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating moisture; or distilling and concentrating at 105 ℃ to obtain concentrated slurry of the graphene composite material.
Particle diameter D of graphene composite material obtained in example 650The particle size of the graphene composite material is 20 microns, graphene is well attached to solid particles of barium chromate-barium sulfate, and the graphene composite material obtained in example 6 is extremely easy to disperse and has a small bulk density.
Example 7:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 4MPa, stirring at a linear speed of 1m/s, and stirring for reacting for 24 h. Stripping for 4 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of the temperature of 70 ℃ and the pressure of 200MPa to generate the graphene dispersion liquid. Then slowly adding barium carbonate into the graphene dispersion liquid at a stirring speed of 10m/s, adjusting the pH value to 6.5, reacting for 2 hours, detecting the pH value again, finely adjusting to 6.5, then performing spray drying or distillation concentration, drying at 180 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 750The particle size is 100 μm, graphene is well attached to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 7 is very easy to disperse and has a low bulk density.
Example 8:
the raw material ratio is 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 dropwise adding concentrated sulfuric acid while stirring, adding expanded graphite after completely and uniformly mixing, uniformly stirring again, pressurizing with air at 7MPa at the stirring speed of 0.2m/s, and stirring for reaction for 12 h. Stripping for 2 times by using a temperature-controllable high-pressure homogenizing dispersion machine under the stripping conditions of 60 ℃ and 180MPa to generate the graphene dispersion liquid. Then slowly adding basic barium carbonate into the graphene dispersion liquid at a stirring speed of 1m/s, adjusting the pH value to 7.5, reacting for 24 hours, detecting the pH value again, finely adjusting to 7.5, then performing spray drying or distillation concentration, drying at 200 ℃, collecting powder to obtain a graphene composite material, and recovering cooling and fractionating 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 850The particle size is 1000 μm, graphene is well attached to the solid barium chromate-barium sulfate particles, and the graphene composite material obtained in example 8 is very easy to disperse and has a low bulk density.
The above examples of the present application are merely examples provided for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a graphene composite material is characterized by comprising the following steps:
dissolving chromium trioxide with a first molar amount in water with a second molar amount to form a chromic acid solution, slowly adding concentrated sulfuric acid with a third molar amount dropwise into the chromic acid solution while stirring, and stirring until the mixture is uniformly mixed to form a mixed solution;
adding a fourth molar amount of expanded graphite to the mixed solution to form a mixed system of intercalated graphite compositions under the first stirring condition;
treating the mixed system under a specified stripping condition, and carrying out high-pressure homogenizing stripping on the intercalated graphite composition to obtain a graphene mixed solution;
under a second stirring condition, forming a suspension by adding alkali barium salt in the graphene mixed solution, and slowly adjusting the pH value of the suspension to be close to a neutral range by adding basic salt of barium;
carrying out spray drying on 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 of preparing a graphene composite material according to claim 1, wherein the fourth molar amount: first molar amount: third molar amount: the ratio of the second molar amount is 10 (1-10) to 1-5 to 45-70.
3. The preparation method of the graphene composite material according to claim 1, wherein the first stirring condition comprises a pressure range of 4 MPa-8 MPa, a stirring speed of 0.2 m/s-1 m/s, and a stirring reaction time of 0.5 h-24 h.
4. The preparation method of the graphene composite material according to claim 3, wherein the first stirring condition comprises a pressure range of 6 MPa-8 MPa, a stirring speed of 0.5 m/s-1 m/s, and a stirring reaction time of 12 h.
5. The preparation method of the graphene composite material according to claim 1, wherein the specified stripping conditions include a stripping high-pressure range of 150MPa to 200MPa, a stripping temperature range of 10 ℃ to 80 ℃, and a high-pressure homogeneous stripping number of 2 to 5.
6. The preparation method of the graphene composite material according to claim 5, wherein the specified stripping conditions include a stripping high-pressure range of 180MPa to 200MPa, a stripping temperature range of 20 ℃ to 60 ℃ and a high-pressure homogeneous stripping number of 3 to 4.
7. The method of preparing a graphene composite material according to claim 1, wherein the basic barium salt includes one or more of barium hydroxide, barium carbonate, and basic barium carbonate.
8. The preparation method of the graphene composite material according to claim 1, wherein the drying temperature range of the spray drying is 50 ℃ to 200 ℃, and the temperature range of the distillation concentration is 50 ℃ to 120 ℃.
9. A graphene composite material prepared by the preparation method of the graphene composite material according to any one of claims 1 to 8, 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 material is 1: 0.2-1: 1.5.
10. The graphene composite material according to claim 9, wherein the particle size of the barium chromate-barium sulfate is 5nm to 1 mm.
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