CN114655948A - Preparation method of small-size graphene dispersion liquid - Google Patents
Preparation method of small-size graphene dispersion liquid Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of graphene dispersion liquid, in particular to a preparation method of small-size graphene dispersion liquid, and provides the following scheme aiming at the problems that the dispersion stability of the prepared graphene dispersion liquid is poor and the application of the graphene dispersion liquid is limited due to single composition of a used raw material graphene in the current preparation technology of the graphene dispersion liquid, wherein the scheme comprises the following steps: s1: preparation, S2: preparation was carried out, S3: detection, S4: final preparation, S5: the invention aims to provide a method for preparing a stable dispersion liquid of small-size graphene, which can be used for large-scale production, does not use strong acid or strong oxidant, does not add a dispersing agent, does not contain metal ions, and avoids negative effects on other application systems, so that various characteristics of graphene are improved, the concentration of the dispersion liquid of small-size graphene is improved, and the application cost is reduced.
Description
Technical Field
The invention relates to the technical field of preparation of graphene dispersion liquid, in particular to a preparation method of small-size graphene dispersion liquid.
Background
At present, graphene has exhibited great performance advantages and application prospects in the fields of plastics, fibers, electric conduction, heat dissipation and the like. The small-size graphene has very high specific surface area, and provides a large number of contact sites for the compounding of the graphene and other materials. The graphene has excellent performances of electric conduction, heat conduction, antibiosis, bacteriostasis, far infrared emission, ultraviolet protection and the like, so that the small-size graphene is easier to use in the fields of electric conduction and heat conduction composite materials, heat dissipation coatings, electric conduction additives, modified fibers, modified plastics and the like. The existing methods for preparing graphene mainly comprise a chemical oxidation-reduction method, a vapor deposition method and a liquid phase stripping method. Although the chemical redox method can realize macroscopic preparation, the defects caused by oxidation cannot be completely recovered, and the conductivity of the conductive material is influenced. The graphene prepared by the vapor deposition method has high quality, but has harsh conditions and high cost, and is not suitable for large-scale production. The liquid phase stripping method can disperse graphite into a specific solvent or surfactant to prepare single-layer or multi-layer graphene through the energy of ultrasonic waves, the graphene dispersion liquid obtained through the method contains a large amount of additives, the additives have very serious negative effects on other application systems, and various characteristics of the graphene can be reduced, so that the graphene cannot be really applied to research in various fields.
However, in the existing preparation technology of the graphene dispersion liquid, the problem that the prepared graphene dispersion liquid is poor in dispersion stability due to the fact that the used raw material graphene is single in composition exists, and the application of the graphene dispersion liquid is limited is solved, so that a preparation method of the small-size graphene dispersion liquid is provided for solving the problem.
Disclosure of Invention
The invention aims to solve the problems that the dispersion stability of a prepared graphene dispersion liquid is poor and the application of the graphene dispersion liquid is limited due to single composition of a used raw material graphene in the existing preparation technology of the graphene dispersion liquid, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a small-size graphene dispersion liquid comprises the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, and processing the selected raw materials;
s2: the preparation is carried out: mixing and other processing selected laminar graphite and water by a professional to prepare a small-size graphene aqueous dispersion;
s3: and (3) detection: detecting the prepared small-size graphene aqueous dispersion;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution;
s5: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, screening according to detection results, and storing the screened graphene aqueous dispersion;
preferably, in S1, a professional selects lamellar graphite and water as raw materials for preparation, where the lamellar graphite includes flake graphite, expanded graphite, and graphite nanoplatelets, and the professional performs screening processing on the selected lamellar graphite, where the screening requirements include that the fixed carbon content of the lamellar graphite is greater than 99% and the particle size D50 is less than 50.0um, tests are performed on the lamellar graphite meeting the screening requirements, material selection is performed according to the test results, and lamellar graphite having a fixed carbon content of greater than 99.95% and a particle size of less than 10um is preferably selected when the material selection is performed;
preferably, in S2, a professional mixes the selected layered graphite with water, and shears, emulsifies, and homogenizes the mixture at an ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the layered graphite to the water is 1-10: 90-98, wherein when the ultrahigh pressure homogenization is carried out, the high pressure homogenization pressure data is set to 1000-4000bar, the homogenization pass is more than 3 times, the more the homogenization pass is, the higher the viscosity is, the larger the particle size D50 is, the pressure data is set to 2000-3500bar, and the homogenization pass is 4-6 times;
preferably, in S3, the prepared small-sized graphene aqueous dispersion is subjected to primary detection, and is judged according to detection data, and is processed according to a judgment result, wherein the detection data shows that the viscosity of the prepared small-sized graphene aqueous dispersion is within the range of 3000-10000mpa.s, the particle size D50 of the graphene tested by a laser particle size analyzer is greater than 10.0um, the preparation success is judged when the vertical thickness tested by an atomic force microscope is less than 4nm, the detection data shows that the viscosity of the prepared small-sized graphene aqueous dispersion is not within the range of 3000-10000mpa.s, the particle size D50 of the graphene tested by the laser particle size analyzer is less than or equal to 10.0um, the preparation failure is judged when the vertical thickness tested by the atomic force microscope is greater than or equal to 4nm, the prepared small-sized graphene aqueous dispersion is collected when the preparation success is judged, the prepared small-sized graphene aqueous dispersion is subjected to waste liquid recovery when the preparation failure is judged, detecting the collected small-size graphene aqueous dispersion again by professional personnel, selecting dispersion with the viscosity of 5000-8000mpa.S, the laser granularity D50 being more than 20um and the vertical thickness being less than 3nm according to the detection result, selecting dispersion with the vertical thickness being less than 2.5nm according to the vertical thickness, preserving the heat of the selected graphene aqueous dispersion, manually detecting the homogenizing temperature by an infrared thermometer during heat preservation, judging according to the detection result, processing according to the judgment result, judging that the homogenizing temperature is in the range of 0-80 ℃ as normal according to the detection result, judging that the homogenizing temperature is not in the range of 0-80 ℃ as abnormal according to the detection result, heating the dispersion in a water bath when the water bath heating is carried out, keeping the water temperature at 70 ℃ when the water bath heating is carried out, heating the dispersion collection container when the water bath heating is judged as abnormal, wherein the water temperature is kept at 85 ℃ when the water bath heating is carried out;
preferably, in S4, the prepared graphene aqueous dispersion is processed to prepare a stable graphene aqueous solution, wherein the processing is performed by preparing the superoxide anion generated by the active oxygen generating device into nano bubbles, and the active oxygen processing time is 1-40h, and the prepared nano bubbles are mixed with ozone, wherein the mixing ratio of the nano bubbles to the ozone is 1-20:reacting superoxide anion with ozone by mixing to generate ozone anion, and generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals OH, wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase through the formed non-covalent effect to obtain a stable graphene aqueous solution, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generating device is 0-70 ℃;
preferably, in S5, the prepared small-sized graphene aqueous dispersion is detected, and screening is performed according to the detection result, wherein the screening is performed when the viscosity is 50-2000mpa.s, wherein the viscosity is preferably 100-500mpa.s, and the carbon-oxygen ratio of the graphene is 97-100: 3-0, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
Compared with the prior art, the invention has the beneficial effects that:
1. by providing the method for preparing the small-size graphene stable dispersion liquid, large-scale production can be realized, strong acid or strong oxidant is not used, dispersing agent is not added, metal ions are not generated, and negative effects on other application systems are avoided, so that various characteristics of graphene are improved, the concentration of the small-size graphene dispersion liquid is improved, and the application cost is reduced.
The invention aims to provide a method for preparing a stable dispersion liquid of small-size graphene, which can be used for large-scale production, does not use strong acid or strong oxidant, does not add a dispersing agent, does not have metal ions, and avoids negative effects on other application systems, so that various characteristics of graphene are improved, the concentration of the dispersion liquid of small-size graphene is improved, and the application cost is reduced.
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Fig. 1 is a flowchart of a preparation method of a small-sized graphene dispersion according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example one
Referring to fig. 1, a method for preparing a small-sized graphene dispersion liquid includes the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, wherein the layered graphite comprises crystalline flake graphite, expanded graphite and graphite nanosheets, screening the selected layered graphite by the professionals, wherein the screening requirements are that the fixed carbon content of the layered graphite is more than 99%, and the granularity D50 is less than 50.0um, testing the layered graphite meeting the screening requirements, selecting materials according to the test results, and preferentially selecting the layered graphite with the fixed carbon content of more than 99.95% and the granularity of less than 10um when selecting the materials;
s2: the preparation is carried out: mixing selected laminar graphite with water by a professional, and shearing, emulsifying and homogenizing the formed mixture under ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the laminar graphite to the water is 1-10: 90-98, wherein when the ultrahigh pressure homogenization is carried out, the high pressure homogenization pressure data is set to 1000-4000bar, the homogenization pass is more than 3 times, the more the homogenization pass is, the higher the viscosity is, the larger the particle size D50 is, the pressure data is set to 2000-3500bar, and the homogenization pass is 4-6 times;
s3: and (3) detection: performing primary detection on the prepared small-size graphene aqueous dispersion, judging through detection data, processing through a judgment result, wherein the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by a laser particle sizer is more than 10.0um, the preparation success is judged if the vertical thickness of the graphene tested by an atomic force microscope is less than 4nm, the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is not within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged if the vertical thickness of the graphene tested by the atomic force microscope is more than or equal to 4nm, the prepared small-size graphene aqueous dispersion is collected if the preparation success is judged, the prepared small-size graphene aqueous dispersion is subjected to waste liquor recovery if the preparation failure is judged, and the collected small-size graphene aqueous dispersion is detected again by a professional, and the viscosity is selected to be 5000-, wherein if the vertical thickness is less than 2.5nm, the dispersion liquid with the vertical thickness less than 2.5nm is selected, the selected graphene water dispersion liquid is subjected to heat preservation, wherein, during the heat preservation, the homogenization temperature is manually detected by an infrared thermometer, and is judged according to the detection result and processed according to the judgment result, wherein the detection result is that the homogenization temperature is within 0-80 deg.C, the detection result is that the homogenization temperature is not within 0-80 deg.C, the detection result is abnormal, and the detection result is normal, the dispersion liquid collecting container is heated in water bath, wherein the water temperature is kept at 70 ℃ when water bath heating is carried out, and water bath heating is carried out on the dispersion liquid collecting container when abnormal condition is judged, wherein the water temperature is kept at 85 ℃ when water bath heating is carried out;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution, wherein during treatment, superoxide anions generated by an active oxygen generating device are prepared into nano bubbles, the active oxygen treatment time is 1-40h, and the prepared nano bubbles are mixed with ozone, wherein the mixing ratio of the nano bubbles to the ozone during mixing is 1-20: 1, mixing and reacting superoxide anion with ozone to generateOzone anion, and simultaneously generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals OH, wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase through the formed non-covalent effect to obtain a stable graphene aqueous solution, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generating device is 0-70 ℃;
s5: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, and screening according to the detection result, wherein the screening requirement is 50-2000mpa.S in the screening process, the preferable viscosity is 100-500mpa.S, and the carbon-oxygen ratio of the graphene is 97-100: 0-3, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
Example two
Referring to fig. 1, a preparation method of a small-sized graphene dispersion liquid includes the following steps:
s1: the preparation is carried out: mixing selected laminar graphite with water by a professional, and shearing, emulsifying and homogenizing the formed mixture under ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the laminar graphite to the water is 1-10: 90-98, wherein when the ultrahigh pressure homogenization is carried out, the high pressure homogenization pressure data is set to 1000-4000bar, the homogenization pass is more than 3 times, the more the homogenization pass is, the higher the viscosity is, the larger the particle size D50 is, the pressure data is set to 2000-3500bar, and the homogenization pass is 4-6 times;
s2: and (3) detection: performing primary detection on the prepared small-size graphene aqueous dispersion, judging through detection data, processing through a judgment result, wherein the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by a laser particle sizer is more than 10.0um, the preparation success is judged if the vertical thickness of the graphene tested by an atomic force microscope is less than 4nm, the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is not within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged if the vertical thickness of the graphene tested by the atomic force microscope is more than or equal to 4nm, the prepared small-size graphene aqueous dispersion is collected if the preparation success is judged, the prepared small-size graphene aqueous dispersion is subjected to waste liquor recovery if the preparation failure is judged, and the collected small-size graphene aqueous dispersion is detected again by a professional, and the viscosity is selected to be 5000-, wherein if the vertical thickness is less than 2.5nm, the dispersion liquid with the vertical thickness less than 2.5nm is selected, the selected graphene water dispersion liquid is subjected to heat preservation, wherein, during the heat preservation, the homogenization temperature is manually detected by an infrared thermometer, and is judged according to the detection result and processed according to the judgment result, wherein the detection result is that the homogenization temperature is within 0-80 deg.C, the detection result is that the homogenization temperature is not within 0-80 deg.C, the detection result is abnormal, and the detection result is normal, the dispersion liquid collecting container is heated in water bath, wherein the water temperature is kept at 70 ℃ when water bath heating is carried out, and water bath heating is carried out on the dispersion liquid collecting container when abnormal condition is judged, wherein the water temperature is kept at 85 ℃ when water bath heating is carried out;
s3: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution, wherein the treatment is carried out by preparing superoxide anions generated by an active oxygen generating device into nano bubbles for 1-40h, and treating the prepared nano bubblesMixing the bubbles with ozone, wherein the mixing ratio of the nano bubbles to the ozone is 1-20: reacting superoxide anion with ozone by mixing to generate ozone anion, and generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals OH, wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase through the formed non-covalent effect to obtain a stable graphene aqueous solution, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generating device is 0-70 ℃;
s4: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, and screening according to the detection result, wherein the screening requirement is 50-2000mpa.S in the screening process, the preferable viscosity is 100-500mpa.S, and the carbon-oxygen ratio of the graphene is 97-100: 0-3, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
EXAMPLE III
Referring to fig. 1, a method for preparing a small-sized graphene dispersion liquid includes the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, wherein the layered graphite comprises crystalline flake graphite, expanded graphite and graphite nanosheets, screening the selected layered graphite by the professionals, wherein the screening requirements are that the fixed carbon content of the layered graphite is more than 99%, and the granularity D50 is less than 50.0um, testing the layered graphite meeting the screening requirements, selecting materials according to the test results, and preferentially selecting the layered graphite with the fixed carbon content of more than 99.95% and the granularity of less than 10um when selecting the materials;
s2: the preparation is carried out: mixing selected laminar graphite with water by a professional, and shearing, emulsifying and homogenizing the formed mixture under ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the laminar graphite to the water is 1-10: 90-98;
s3: and (3) detection: performing primary detection on the prepared small-size graphene aqueous dispersion, judging through detection data, processing through a judgment result, wherein the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is within 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by a laser particle sizer is more than 10.0um, the preparation success is judged if the vertical thickness of the graphene tested by an atomic force microscope is less than 4nm, the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is not within 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged if the vertical thickness of the graphene tested by the atomic force microscope is more than or equal to 4nm, the prepared small-size graphene aqueous dispersion is collected if the preparation success is judged, the prepared small-size graphene aqueous dispersion is subjected to waste liquid recovery if the preparation failure is judged, and the collected small-size graphene aqueous dispersion is detected again by a professional, and the viscosity is selected to be 5000-, wherein if the vertical thickness is less than 2.5nm, the dispersion liquid with the vertical thickness less than 2.5nm is selected, the selected graphene water dispersion liquid is subjected to heat preservation, wherein, during the heat preservation, the homogenization temperature is manually detected by an infrared thermometer, and is judged according to the detection result and processed according to the judgment result, wherein the detection result is that the homogenization temperature is within 0-80 deg.C, the detection result is that the homogenization temperature is not within 0-80 deg.C, the detection result is abnormal, and the detection result is normal, the water bath heating is performed on the dispersion liquid collecting container, wherein the water temperature is kept at 70 ℃ when water bath heating is carried out, and water bath heating is carried out on the dispersion liquid collecting container when abnormal condition is judged, wherein the water temperature is kept at 85 ℃ when water bath heating is carried out;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution, wherein during treatment, superoxide anions generated by an active oxygen generating device are prepared into nano bubbles, the active oxygen treatment time is 1-40h, and the prepared nano bubbles are mixed with ozone, wherein the mixing ratio of the nano bubbles to the ozone during mixing is 1-20: reacting superoxide anion with ozone by mixing to generate ozone anion, and generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals OH, wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase through the formed non-covalent effect to obtain a stable graphene aqueous solution, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generating device is 0-70 ℃;
s5: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, and screening according to the detection result, wherein the screening requirement is 50-2000mpa.S in the screening process, the preferable viscosity is 100-500mpa.S, and the carbon-oxygen ratio of the graphene is 97-100: 0-3, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
Example four
Referring to fig. 1, a preparation method of a small-sized graphene dispersion liquid includes the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, wherein the layered graphite comprises crystalline flake graphite, expanded graphite and graphite nanosheets, screening the selected layered graphite by the professionals, wherein the screening requirements are that the fixed carbon content of the layered graphite is more than 99%, and the granularity D50 is less than 50.0um, testing the layered graphite meeting the screening requirements, selecting materials according to the test results, and preferentially selecting the layered graphite with the fixed carbon content of more than 99.95% and the granularity of less than 10um when selecting the materials;
s2: the preparation is carried out: mixing selected laminar graphite with water by a professional, and shearing, emulsifying and homogenizing the formed mixture under ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the laminar graphite to the water is 1-10: 90-98, wherein when the ultrahigh pressure homogenization is carried out, the high pressure homogenization pressure data is set to 1000-4000bar, the homogenization pass is more than 3 times, the more the homogenization pass is, the higher the viscosity is, the larger the particle size D50 is, the pressure data is set to 2000-3500bar, and the homogenization pass is 4-6 times;
s3: and (3) detection: performing primary detection on the prepared small-size graphene aqueous dispersion, judging through detection data, processing through a judgment result, wherein the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is within 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by a laser particle sizer is more than 10.0um, the preparation success is judged if the vertical thickness of the graphene tested by an atomic force microscope is less than 4nm, the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is not within 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged if the vertical thickness of the graphene tested by the atomic force microscope is more than or equal to 4nm, the prepared small-size graphene aqueous dispersion is collected if the preparation success is judged, the prepared small-size graphene aqueous dispersion is subjected to waste liquid recovery if the preparation failure is judged, and the collected small-size graphene aqueous dispersion is detected again by a professional, and the viscosity is selected to be 5000-, wherein if the vertical thickness is less than 2.5nm, the dispersion liquid with the vertical thickness less than 2.5nm is selected, the selected graphene water dispersion liquid is subjected to heat preservation, wherein, during the heat preservation, the homogenization temperature is manually detected by an infrared thermometer, and is judged according to the detection result and is processed according to the judgment result, wherein the detection result is that the homogenization temperature is within 0-80 deg.C, the detection result is that the homogenization temperature is not within 0-80 deg.C, the detection result is abnormal, and the detection result is normal, the dispersion liquid collecting container is heated in water bath, wherein the water temperature is kept at 70 ℃ when water bath heating is carried out, and water bath heating is carried out on the dispersion liquid collecting container when abnormal condition is judged, wherein the water temperature is kept at 85 ℃ when water bath heating is carried out;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution, wherein during treatment, superoxide anions generated by an active oxygen generating device are prepared into nano bubbles, the active oxygen treatment time is 1-40h, and the prepared nano bubbles are mixed with ozone, wherein the mixing ratio of the nano bubbles to the ozone during mixing is 1-20: reacting superoxide anion with ozone by mixing to generate ozone anion, and generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals (OH), wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase to obtain a stable graphene aqueous solution through the formed non-covalent effect, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device or a foam graphene composite carbon nanotube electrode device;
s5: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, and screening according to the detection result, wherein the screening requirement is 50-2000mpa.S in the screening process, the preferable viscosity is 100-500mpa.S, and the carbon-oxygen ratio of the graphene is 97-100: 0-3, standing test results are free of sedimentation, the granularity D97 of the graphene tested by the laser particle size analyzer is less than 5.0um, and the granularity D97 of the graphene tested by the laser particle size analyzer is less than 3.0um, the graphene is selected preferentially, and the screened small-size graphene aqueous dispersion is subjected to a sampling test, wherein the sampling volume when the sampling test is carried out is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
EXAMPLE five
Referring to fig. 1, a method for preparing a small-sized graphene dispersion liquid includes the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, wherein the layered graphite comprises crystalline flake graphite, expanded graphite and graphite nanosheets, screening the selected layered graphite by the professionals, wherein the screening requirements are that the fixed carbon content of the layered graphite is more than 99%, and the granularity D50 is less than 50.0um, testing the layered graphite meeting the screening requirements, selecting materials according to the test results, and preferentially selecting the layered graphite with the fixed carbon content of more than 99.95% and the granularity of less than 10um when selecting the materials;
s2: the preparation is carried out: mixing selected laminar graphite with water by a professional, and shearing, emulsifying and homogenizing the formed mixture under ultrahigh pressure to prepare the small-size graphene aqueous dispersion, wherein the ratio of the laminar graphite to the water is 1-10: 90-98, wherein when the ultrahigh pressure homogenization is carried out, the high pressure homogenization pressure data is set to 1000-4000bar, the homogenization pass is more than 3 times, the more the homogenization pass is, the higher the viscosity is, the larger the particle size D50 is, the pressure data is set to 2000-3500bar, and the homogenization pass is 4-6 times;
s3: and (3) detection: performing primary detection on the prepared small-size graphene aqueous dispersion, judging through detection data, processing through a judgment result, wherein the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by a laser particle sizer is more than 10.0um, the preparation success is judged if the vertical thickness of the graphene tested by an atomic force microscope is less than 4nm, the detection data show that the viscosity of the prepared small-size graphene aqueous dispersion is not within the range of 3000 plus 10000mpa.S, the particle size D50 of the graphene tested by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged if the vertical thickness of the graphene tested by the atomic force microscope is more than or equal to 4nm, the prepared small-size graphene aqueous dispersion is collected if the preparation success is judged, the prepared small-size graphene aqueous dispersion is subjected to waste liquor recovery if the preparation failure is judged, and the collected small-size graphene aqueous dispersion is detected again by a professional, and the viscosity is selected to be 5000-, wherein if the vertical thickness is less than 2.5nm, the dispersion liquid with the vertical thickness less than 2.5nm is selected, the selected graphene water dispersion liquid is subjected to heat preservation, wherein, during the heat preservation, the homogenization temperature is manually detected by an infrared thermometer, and is judged according to the detection result and is processed according to the judgment result, wherein the detection result is that the homogenization temperature is within 0-80 deg.C, the detection result is that the homogenization temperature is not within 0-80 deg.C, the detection result is abnormal, and the detection result is normal, the dispersion liquid collecting container is heated in water bath, wherein the water temperature is kept at 70 ℃ when water bath heating is carried out, and water bath heating is carried out on the dispersion liquid collecting container when abnormal condition is judged, wherein the water temperature is kept at 85 ℃ when water bath heating is carried out;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution, wherein during treatment, superoxide anions generated by an active oxygen generating device are prepared into nano bubbles, the active oxygen treatment time is 1-40h, and the prepared nano bubbles are mixed with ozone, wherein the mixing ratio of the nano bubbles to the ozone during mixing is 1-20: reacting superoxide anion with ozone by mixing to generate ozone anion, and simultaneously passing the generated ozone anionThe ions contact with water to generate hydroxyl free radicals OH to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) performing free radical reaction, namely performing edge oxidation on graphene by using hydroxyl free radicals OH, wherein the edge oxidation is to form a stronger non-covalent effect among graphene sheet layers, and promoting stable dispersion of the graphene sheet layers in a water phase through the formed non-covalent effect to obtain a stable graphene aqueous solution, wherein the active oxygen generating device is a foam graphene electrode device, a foam metal electrode device and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generating device is 0-70 ℃;
s5: and (3) subsequent treatment: detecting the prepared small-size graphene aqueous dispersion, and screening according to the detection result, wherein the screening requirement is 50-2000mpa.S in the screening process, the preferred viscosity is 100-500mpa.S, and the carbon-oxygen ratio of graphene is 97-100: 0-3, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: and 89, acquiring performance data through a graphene granularity test, comparing the acquired performance data with the existing data, calculating the performance improvement rate, and manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized manner after the sampling test is finished.
The preparation method of the small-sized graphene dispersion liquid in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment is tested, and the following results are obtained:
the preparation methods of the small-size graphene dispersions prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment are significantly improved in stability compared with the dispersion prepared by the conventional method, and the first embodiment is the best embodiment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. A preparation method of a small-size graphene dispersion liquid is characterized by comprising the following steps:
s1: preparation is carried out: selecting layered graphite and water as raw materials for preparation by professionals, and treating the selected raw materials;
s2: the preparation is carried out: mixing and other processing selected laminar graphite and water by a professional to prepare a small-size graphene aqueous dispersion;
s3: and (3) detection: detecting the prepared small-size graphene aqueous dispersion;
s4: and (3) final preparation: treating the prepared graphene aqueous dispersion to prepare a stable graphene aqueous solution;
s5: and (3) subsequent treatment: and detecting the prepared small-size graphene aqueous dispersion, screening according to the detection result, and storing the screened graphene aqueous dispersion.
2. The method of claim 1, wherein in S1, layered graphite and water are selected by a professional as raw materials for preparation, wherein the layered graphite comprises flake graphite, expanded graphite and graphite nanoplatelets, and the professional performs a screening process on the selected layered graphite, wherein the screening process requires that the fixed carbon content of the layered graphite is greater than 99% and the particle size D50 is less than 50.0um, tests are performed on the layered graphite meeting the screening requirements, the test results show that the material selection is performed, and when the material selection is performed, layered graphite with the fixed carbon content of greater than 99.95% and the particle size of less than 10um is preferably selected.
3. The method according to claim 1, wherein in step S2, a professional mixes the selected layered graphite with water, and the resulting mixture is subjected to shearing, emulsifying and ultra-high pressure homogenization to obtain the small-sized graphene aqueous dispersion, wherein the ratio of the layered graphite to the water is 1-10: 90-98.
4. The method as claimed in claim 3, wherein the high pressure homogenization pressure data is set at 1000-4000bar, the number of homogenization passes is > 3, the pressure data is set at 2000-3500bar, and the number of homogenization passes is 4-6.
5. The method as claimed in claim 1, wherein in S3, the prepared small-sized graphene aqueous dispersion is primarily detected, and is judged according to the detection data, and the judgment result is processed, wherein the detection data shows that the viscosity of the prepared small-sized graphene aqueous dispersion is within the range of 3000-10000mpa.S, the particle size D50 of the graphene measured by a laser particle sizer is more than 10.0um, the preparation success is judged when the vertical thickness measured by an atomic force microscope is less than 4nm, the detection data shows that the viscosity of the prepared small-sized graphene aqueous dispersion is not within the range of 3000-10000mpa.S, the particle size D50 of the graphene measured by the laser particle sizer is less than or equal to 10.0um, the preparation failure is judged when the vertical thickness measured by the atomic force microscope is more than or equal to 4nm, and the prepared small-sized graphene aqueous dispersion is collected when the preparation success is judged, and if the preparation fails, recovering the waste liquid of the prepared small-size graphene aqueous dispersion.
6. The method as claimed in claim 5, wherein the collected small-sized graphene aqueous dispersion is re-tested by a professional, and the viscosity of the collected small-sized graphene aqueous dispersion is 8000mpa.S, the laser particle size D50 is greater than 20 μm, the vertical thickness of the collected small-sized graphene aqueous dispersion is less than 3nm, and the vertical thickness of the collected small-sized graphene aqueous dispersion is less than 2.5nm, and the selected graphene aqueous dispersion is thermally insulated, wherein the homogeneous temperature is manually tested by an infrared thermometer during thermal insulation, and the test result is processed by the judgment result, wherein the test result is that the homogeneous temperature is within 0-80 ℃ and is normal, the test result is that the homogeneous temperature is not within 0-80 ℃ and is abnormal, and the dispersion collection container is heated in water bath when the test result is normal, wherein the water temperature is maintained at 70 deg.C when water bath heating is performed, and water bath heating is performed on the dispersion collecting container when abnormal condition is determined, wherein the water temperature is maintained at 85 deg.C when water bath heating is performed.
7. The method of claim 1, wherein in step S4, the prepared graphene aqueous dispersion is treated to prepare a stable graphene aqueous solution, wherein the treatment is performed by forming the superoxide anion generated by the active oxygen generating device into nano-bubbles for an active oxygen treatment time of 1-40h, and mixing the nano-bubbles with ozone, wherein the mixing ratio of the nano-bubbles to the ozone is 1-20: reacting superoxide anion with ozone by mixing to generate ozone anion, and generating hydroxyl radical OH by contacting the generated ozone anion with water to increase OH-Interface concentration of (3), graphene and OH-The method comprises the following steps of (1) carrying out edge oxidation on graphene by utilizing hydroxyl radical OH, wherein the edge oxidation is to form a stronger non-covalent effect between graphene sheet layers, and promoting the stable dispersion of the graphene sheet layers in a water phase to obtain a stable graphene aqueous solution through the formed non-covalent effect.
8. The method of claim 7, wherein the active oxygen generator is selected from a group consisting of a foam graphene electrode device, a foam metal electrode device, and a foam graphene composite carbon nanotube electrode device, and the temperature of the active oxygen generator is 0-70 ℃.
9. The method as claimed in claim 1, wherein in S5, the prepared graphene dispersion with small size is detected, and the screening is performed according to the detection result, wherein the screening is performed with a viscosity of 50-2000mpa.s, preferably a viscosity of 100-500mpa.s, and a graphene carbon-to-oxygen ratio of 97-100: 3-0, standing test results are free of settlement, the granularity D97 of graphene tested by a laser particle analyzer is less than 5.0um, and the granularity D97 of graphene tested by the laser particle analyzer is less than 3.0um, then the graphene is preferentially selected, and the screened small-size graphene aqueous dispersion is subjected to sampling test, wherein the sampling volume is as follows: the total volume screened was 1: 89, obtaining performance data through a graphene granularity test, comparing the obtained performance data with the existing data, calculating the performance improvement rate, and after the sampling test is finished, manually collecting and storing the finally screened small-size graphene aqueous dispersion liquid in a centralized way, wherein the storage environment temperature is kept at 15-18 ℃ during storage.
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| CN107082416A (en) * | 2017-04-17 | 2017-08-22 | 中国科学院化学研究所 | A kind of method that graphene is prepared based on ozone oxidation |
| CN109052380A (en) * | 2018-09-10 | 2018-12-21 | 成都紫苑华光新材料科技有限公司 | The method that full liquid water phase physics removing prepares graphene |
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| US20140323596A1 (en) * | 2011-11-30 | 2014-10-30 | Korea Electrotechnology Research Institute | Graphene oxide reduced material dispersed at high concentration by cation-ii interaction and method for manufacturing same |
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| CN107082416A (en) * | 2017-04-17 | 2017-08-22 | 中国科学院化学研究所 | A kind of method that graphene is prepared based on ozone oxidation |
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