WO2021032039A1 - 低粘度的氧化石墨烯浆料及其制备方法、氧化石墨烯膜及其制备方法 - Google Patents
低粘度的氧化石墨烯浆料及其制备方法、氧化石墨烯膜及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 310
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 304
- 239000002002 slurry Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000007613 slurry method Methods 0.000 title 1
- 239000011248 coating agent Substances 0.000 claims abstract description 55
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- 238000000034 method Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000007872 degassing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000009849 vacuum degassing Methods 0.000 claims description 7
- 238000003490 calendering Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000007765 extrusion coating Methods 0.000 claims description 3
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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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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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
- C01B32/198—Graphene oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
Definitions
- the invention relates to the field of graphene materials, in particular to a process for improving the preparation efficiency of a graphene heat conducting film prepared by a thermal reduction method.
- the main method for preparing a graphene thermally conductive film with good thermal conductivity is: firstly disperse the graphene oxide filter cake prepared by the Hummers method into a slurry, coat the slurry on the substrate, and prepare it after drying The graphene oxide film is then subjected to high temperature thermal reduction on the graphene oxide film to obtain a graphene thermally conductive film.
- the technical problem to be solved by the present invention is to improve the efficiency of graphene oxide slurry coating.
- the main method used is to apply graphene oxide through high-pressure shearing, high-speed impact and strong
- the cavitation function of the graphene oxide is ultra-fine, reduces the size of the graphene oxide sheet, reduces the viscosity of the graphene oxide slurry, and increases the solid content of the graphene oxide slurry, thereby improving the coating efficiency of the graphene oxide slurry.
- the present invention provides a low-viscosity graphene oxide slurry, the solid content of the graphene oxide slurry is 5-10%, preferably 8%.
- the viscosity of the graphene oxide slurry is 10000-50000 mPa ⁇ s, preferably 20000 mPa ⁇ s.
- Too high or too low viscosity is not conducive to coating.
- the viscosity is higher than 50000mPa ⁇ s, which is not conducive to the casting of graphene oxide slurry; if the viscosity is lower than 10000mPa ⁇ s, the fluidity of graphene oxide slurry is too large, which is not conducive to control. Coating thickness.
- the low-viscosity graphene oxide slurry is graphene oxide microflakes, with an average sheet diameter of 2-3 ⁇ m.
- the invention also provides a method for preparing low-viscosity graphene oxide slurry.
- Graphene oxide is mixed with a solvent, dispersed, and ultra-fine to reduce the average sheet diameter of graphene oxide to obtain low-viscosity graphene oxide slurry material.
- Graphene oxide contains very rich oxygen-containing functional groups. During the oxidation process, "defects" are generated due to the existence of functional groups at the edge and the middle of the sheet. This part of the defect is easy to be in the high-pressure viscosity reduction equipment (cavitation effect, impact effect shear Effect) is broken under the action of, so that the diameter of the graphene oxide can be reduced from an average of 17-18 ⁇ m to 2-3 ⁇ m. In addition, since the oxygen-containing functional group of graphene oxide has a hydrophilic effect, it can be dispersed in water.
- the graphene oxide is prepared by the Hummers method.
- the molar ratio of oxygen to carbon is 0.6-0.7, preferably 0.65.
- the solvent is water.
- the linear velocity of the dispersion is 2-20 m/s, preferably 5 m/s.
- the dispersion time is 1-5h, preferably 2h.
- the graphene oxide sheets When dispersed, the graphene oxide sheets are opened in water and dispersed evenly.
- the method of ultra-micronization includes applying pressure to a mixture of graphene oxide and a solvent, passing the mixture through a slit, and subjecting the mixture to high-pressure shear and high-speed impact in the process of passing through the slit. Later, due to the instantaneous release of pressure energy, strong cavitation occurs.
- the applied pressure is 50-250 MPa, preferably 100 MPa.
- the graphene oxide is ultra-fine to have an average sheet diameter of 2-3 ⁇ m.
- Ultra-micronization is the use of high pressure to make the liquid material flow through the narrow gap at high speed, the strong cavitation effect similar to the explosion effect is generated in the narrow area under the high pressure that the pressure energy is suddenly released, and the liquid material passes through the slit.
- the chemical action and the high-speed impact produced by the impact in the chamber break the liquid material, so that the liquid substance or the solid particles with the liquid as the carrier are ultra-fine, and the graphene oxide microplates are refined.
- the pressure applied to the mixture of graphene oxide and solvent is 50-250MPa by setting the ultra-fineness, and the sheet diameter of graphene oxide can be refined from 17-18 ⁇ m to 2-3 ⁇ m on average.
- the pressure is too small, less than 50MPa, then If the refining effect is not enough, the graphene oxide sheet diameter cannot reach 2-3 ⁇ m, and the effect of viscosity reduction cannot be achieved; if the pressure is greater than 250MPa, the machine will be easily damaged. The higher the damage frequency, the higher the production cost.
- the viscosity of the graphene oxide slurry before ultra-micronization is 100000-200000 mPa ⁇ s.
- the viscosity of the graphene oxide slurry after ultrafineness is 10000-50000 mPa ⁇ s, preferably 20000 mPa ⁇ s.
- the solid content of the graphene oxide slurry is 5-10%, preferably 8%.
- the present invention also provides a graphene oxide film, the average sheet diameter of the graphene oxide in the graphene oxide film is 2-3 ⁇ m.
- the thickness of the graphene oxide film is 50-500 ⁇ m, preferably 200 ⁇ m.
- the density of the graphene oxide film is 1.0-2.0 g/cm 3 .
- the present invention also provides a method for preparing a graphene oxide film.
- the preparation method of the low-viscosity graphene oxide slurry is used to prepare the low-viscosity graphene oxide slurry. After defoaming treatment, the defoaming oxidation The graphene slurry is coated on the surface of the substrate, dried and peeled off to obtain a graphene oxide film.
- the substrate is a carrier coated and dried by graphene oxide slurry. After the graphene oxide slurry is coated and dried, a graphene oxide film is formed on the surface of the substrate.
- the degassing is vacuum degassing, and the vacuum value of the vacuum degassing is -95 to -50 kPa, preferably -80 kPa.
- the defoaming adopts an online continuous defoaming machine.
- the coating adopts knife coating or extrusion coating, and the coating rate is 1-10 m/min, preferably 3 m/min.
- the thickness of the coating is 0.5-5.0 mm, preferably 1.5 mm.
- the drying temperature is 70-130°C, preferably 100°C.
- the drying time is 8-80 min, preferably 27-30 min.
- the thickness of the graphene oxide film is 50-500 ⁇ m, preferably 200 ⁇ m.
- the coating thickness becomes thinner, the coating speed increases, and the coating efficiency per unit time increases.
- the drying time is adjusted according to the length of the oven of the coating machine and the coating speed. The drying time is shortened due to the increase of the coating speed, which greatly improves the preparation efficiency of the graphene oxide film.
- the present invention also provides a graphene thermally conductive film, the thermal conductivity of the graphene thermally conductive film is 1000-1600 W/m ⁇ k, preferably 1500 W/m ⁇ k.
- the thermally conductive graphene film density of 1.5-2.2g / cm 3, preferably 2.0g / cm 3.
- the thickness of the graphene thermally conductive film is 10-150 ⁇ m, preferably 40 ⁇ m.
- the invention also provides a method for preparing a graphene thermally conductive film.
- the graphene oxide film is prepared by adopting the method for preparing a graphene oxide film, and the graphene thermally conductive film is obtained by heat treatment and rolling.
- the temperature of the heat treatment is 1000-3000°C, preferably 2000°C.
- the density after the heat-treated graphene oxide film of 0.1-1.0g / cm 3, preferably 0.3g / cm 3.
- the pressure of the calendering is 50-200t, preferably 100t.
- the graphene oxide microplates are refined to reduce the diameter of the graphene oxide from an average of 17-18 ⁇ m to 2-3 ⁇ m, reduce the viscosity of the graphene oxide slurry, and increase the solid content of the slurry to 5-10 %.
- the drying can be carried out at a higher temperature without bubbling the graphene oxide film; in addition, the water content of the graphene oxide slurry becomes lower, so that the graphite oxide
- the olefin film is easier to remove water molecules, reduces the drying time, and improves the efficiency of preparing the graphene oxide film.
- the graphene thermally conductive film prepared by the present invention has normal appearance, thickness, density, thermal conductivity, cohesion and other performance tests.
- Figure 1 is a schematic diagram of AFM before graphene oxide sheet diameter reduction
- Figure 2 is a schematic diagram of AFM after graphene oxide sheet diameter reduction
- Figure 3 is a graph of the AFM particle size distribution of graphene oxide before viscosity reduction, the abscissa represents the size of the graphene oxide sheet diameter ( ⁇ m), and the ordinate represents the frequency (number);
- Figure 4 is a graph of the AFM particle size distribution of graphene oxide after viscosity reduction, the abscissa represents the size of the graphene oxide sheet diameter ( ⁇ m), and the ordinate represents the frequency (number);
- Figure 5 is a step diagram of a sixth embodiment of the present invention.
- Example 6 is a physical diagram of the graphene oxide film of Example 1.
- FIG. 7 is a physical diagram of the graphene thermally conductive film of Example 1.
- Example 8 is a physical diagram of the graphene oxide film of Example 2.
- Figure 10 is a physical view of the graphene oxide film of Comparative Example 5.
- Fig. 12 is a physical diagram of a graphene oxide film with bubbling generated when a 6.0mm thick graphene oxide film is dried at 100°C.
- a low-viscosity graphene oxide slurry is shown.
- the solid content of the graphene oxide slurry is 5-10%, for example: 5%, 5.5%, 6%, 6.5% , 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc.
- the solid content of the graphene oxide slurry is 8%.
- the viscosity of graphene oxide slurry is 10000-50000mPa ⁇ s, for example: 10000mPa ⁇ s, 11000mPa ⁇ s, 12000mPa ⁇ s, 15000mPa ⁇ s, 20000mPa ⁇ s, 22000mPa ⁇ s, 23000mPa ⁇ s, 25000mPa ⁇ s, 30000mPa ⁇ s s, 32000mPa ⁇ s, 35000mPa ⁇ s, 40000mPa ⁇ s, 42000mPa ⁇ s, 45000mPa ⁇ s, 48000mPa ⁇ s, 50000mPa ⁇ s, etc.
- the viscosity of the graphene oxide slurry is 20000 mPa ⁇ s.
- Too high or too low viscosity is not conducive to coating.
- the viscosity is higher than 50000mPa ⁇ s, which is not conducive to the outflow of graphene oxide slurry; if the viscosity is lower than 10000mPa ⁇ s, the fluidity of graphene oxide slurry is too large, which is not conducive to control coating. Thickness of cloth.
- Graphene oxide is graphene oxide microplates with an average sheet diameter of 2-3 ⁇ m, such as: 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, 3 ⁇ m ,Wait.
- Graphene oxide is mixed with a solvent, dispersed, and ultra-fine to reduce the average sheet diameter of graphene oxide. A low-viscosity graphene oxide slurry is obtained.
- Graphene oxide contains very rich oxygen-containing functional groups. During the oxidation process, "defects" are generated due to the existence of functional groups at the edge and the middle of the lamella. This part of the defect is easy to be caused by high-pressure viscosity reduction equipment (cavitation effect, impact effect) It is broken under the action, so that the sheet diameter of graphene oxide is reduced from an average of 17-18 ⁇ m to 2-3 ⁇ m. In addition, since the oxygen-containing functional group of graphene oxide has a hydrophilic effect, it can be dispersed in water.
- Graphene oxide is prepared by the Hummers method.
- the molar ratio of oxygen to carbon is 0.6-0.7, for example: 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, etc.
- the molar ratio of oxygen to carbon in graphene oxide is 0.65.
- the solvent is water.
- the dispersed linear velocity is 2-20m/s, for example: 2m/s, 3m/s, 4m/s, 5m/s, 6m/s, 7m/s, 8m/s, 9m/s, 10m/s, 11m /s, 12m/s, 13m/s, 14m/s, 15m/s, 16m/s, 17m/s, 18m/s, 19m/s, 20m/s, etc.
- the linear velocity of dispersion is 5 m/s.
- the dispersion time is 1-5h, for example: 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h , 4.8h, 5h, etc.
- the dispersion time is 2h.
- the method of ultra-micronization includes applying pressure to the mixture of graphene oxide and solvent, passing the mixture through a slit, and subjecting the mixture to high-pressure shear and high-speed impact during the process of passing through the slit, and after passing through the slit, due to the sudden pressure energy Release and produce a strong cavitation effect.
- the applied pressure is 50-250MPa, for example: 50MPa, 51MPa, 52MPa, 53MPa, 54MPa, 55MPa, 56MPa, 57MPa, 58MPa, 59MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, 160MPa, 170MPa, 180MPa, 190MPa, 200MPa, 210MPa, 220MPa, 230MPa, 240MPa, 245MPa, 246MPa, 247MPa, 248MPa, 249MPa, 250MPa, etc.
- the pressure for ultra-micronization is 100 MPa.
- the average sheet diameter of ultra-fine graphene oxide is 2-3 ⁇ m, for example: 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, 3 ⁇ m, etc. .
- Figure 1 compared with the 50 ⁇ m scale, the graphene oxide has a larger sheet diameter, and some graphene oxide sheets can reach 25 ⁇ m in diameter.
- the bar scale on the right represents the height of graphene oxide.
- the sheet diameter of graphene oxide is very small, basically less than 3 ⁇ m, and the bar scale on the right represents the height of graphene oxide.
- the sheet diameters of graphene oxide before viscosity reduction are concentrated in the interval of 15-25 ⁇ m, the average sheet diameter is 18.236 ⁇ m, and the standard deviation is 1.012; the sheet diameters of graphene oxide after viscosity reduction are concentrated In the interval of 1.6-4 ⁇ m, the average sheet diameter is 2.495 ⁇ m, and the standard deviation is 0.936. After viscosity reduction, the sheet diameter of graphene oxide decreases, and the sheet diameter distribution is more even.
- Ultra-micronization is the use of high pressure to make the liquid material flow through the narrow gap at high speed, the strong cavitation effect similar to the explosion effect is generated in the narrow area under the high pressure that the pressure energy is suddenly released, and the liquid material passes through the slit.
- the chemical action and the high-speed impact produced by the impact in the chamber break the liquid material, so that the liquid substance or the solid particles with the liquid as the carrier are ultra-fine, and the graphene oxide microplates are refined.
- the pressure applied to the mixture of graphene oxide and solvent is 50-250MPa by setting the ultra-micronization, and the sheet diameter of graphene oxide can be refined from 17-18 ⁇ m on average to 2-3 ⁇ m.
- the pressure is too small, less than 50MPa, If the refining effect is not enough, the graphene oxide sheet diameter cannot reach 2-3 ⁇ m, and the viscosity reduction effect cannot be achieved; if the pressure is greater than 250MPa, the machine will be easily damaged. The higher the damage frequency, the higher the production cost.
- the viscosity of graphene oxide slurry before ultra-micronization is 100000-200000mPa ⁇ s, for example: 100000mPa ⁇ s, 105000mPa ⁇ s, 110000mPa ⁇ s, 115000mPa ⁇ s, 120000mPa ⁇ s, 125000mPa ⁇ s, 130000mPa ⁇ s, 135000mPa ⁇ S, 140000mPa ⁇ s, 145000mPa ⁇ s, 150000mPa ⁇ s, 160000mPa ⁇ s, 170000mPa ⁇ s, 180000mPa ⁇ s, 190000mPa ⁇ s, 195000mPa ⁇ s, 200,000mPa ⁇ s, etc.
- the viscosity of graphene oxide slurry after ultra-fine refinement is 10000-50000mPa ⁇ s, for example: 10000mPa ⁇ s, 11000mPa ⁇ s, 12000mPa ⁇ s, 15000mPa ⁇ s, 20000mPa ⁇ s, 22000mPa ⁇ s, 23000mPa ⁇ s, 25000mPa ⁇ S, 30000mPa ⁇ s, 32000mPa ⁇ s, 35000mPa ⁇ s, 40000mPa ⁇ s, 42000mPa ⁇ s, 45000mPa ⁇ s, 48000mPa ⁇ s, 50000mPa ⁇ s, etc.
- the viscosity of the graphene oxide slurry after being ultrafine is 20000 mPa ⁇ s.
- the solid content of graphene oxide slurry is 5-10%, for example: 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5 %, 9%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, etc.
- the solid content of the graphene oxide slurry is 8%.
- a graphene oxide film is shown.
- the average sheet diameter of the graphene oxide in the graphene oxide film is 2-3 ⁇ m, for example: 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, 3 ⁇ m, etc.
- the thickness of the graphene oxide film is 100-500 ⁇ m, for example: 100 ⁇ m, 120 ⁇ m, 150 ⁇ m, 180 ⁇ m, 200 ⁇ m, 220 ⁇ m, 250 ⁇ m, 280 ⁇ m, 300 ⁇ m, 320 ⁇ m, 350 ⁇ m, 380 ⁇ m, 400 ⁇ m, 420 ⁇ m, 450 ⁇ m, 480 ⁇ m, 500 ⁇ m, etc.
- the thickness of the graphene oxide film is 200 ⁇ m.
- the density of the graphene oxide film is 1.0-2.0g/cm 3 , for example: 1.0g/cm 3 , 1.1g/cm 3 , 1.2g/cm 3 , 1.3g/cm 3 , 1.4g/cm 3 , 1.5g/ cm 3 , 1.6g/cm 3 , 1.7g/cm 3 , 1.8g/cm 3 , 1.9g/cm 3 , 2.0g/cm 3 , etc.
- a method for preparing graphene oxide film is shown.
- the method of the second embodiment of the present invention is used to prepare a low-viscosity graphene oxide slurry.
- the defoamed graphene oxide slurry is coated on the surface of the substrate, dried and peeled off to obtain a graphene oxide film.
- the substrate is a carrier coated and dried by graphene oxide slurry. After the graphene oxide slurry is coated and dried, a graphene oxide film is formed on the surface of the substrate.
- Degassing is vacuum degassing.
- the vacuum value of vacuum degassing is -95 to -50kPa, for example: -95kPa, 90kPa, -85kPa, -80kPa, -75kPa, -70kPa, -65kPa, -60kPa, -55kPa, -50kPa ,Wait.
- the vacuum value of vacuum degassing is -80 kPa.
- the deaeration adopts an online continuous deaeration machine.
- Coating adopts knife coating or extrusion coating, and the coating speed is 1-10m/min, for example: 1m/min, 1.1m/min, 1.2m/min, 1.3m/min, 1.4m/min , 1.5m/min, 2m/min, 2.5m/min, 3m/min, 3.5m/min, 4m/min, 4.5m/min, 5m/min, 5.5m/min, 6m/min, 6.5m/min , 7m/min, 7.5m/min, 8m/min, 8.5m/min, 9m/min, 9.5m/min, 9.6m/min, 9.7m/min, 9.8m/min, 9.9m/min, 10m/ min, wait.
- the coating rate is 3m/min.
- the coating thickness is 0.5-5.0mm, for example: 0.5mm, 0.52mm, 0.55mm, 0.58mm, 0.6mm, 0.62mm, 0.65mm, 0.68mm, 0.7mm, 0.75mm, 0.76mm, 0.77mm, 0.78mm , 0.79mm, 0.8mm, 0.9mm, 1mm, 1.2mm, 1.3mm, 1.5mm, 1.6mm, 1.8mm, 2mm, 2.1mm, 2.2mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, 2.93mm, 2.95mm, 2.97mm, 2.98mm, 2.99mm, 3.0mm, 3.5mm, 4mm, 4.2mm, 4.5mm, 4.8mm, 5mm, etc.
- the thickness of the coating is 1.5 mm. As the solid content of the graphene oxide slurry increases, the coating thickness becomes thinner, the coating speed increases, and the coating efficiency per unit time increases.
- the drying temperature is 70-130°C, for example: 70°C, 71°C, 72°C, 73°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C ⁇ 100°C ⁇ 102°C ⁇ 105°C ⁇ 108°C ⁇ 110°C ⁇ 112°C ⁇ 115°C ⁇ 118°C ⁇ 120°C ⁇ 122°C ⁇ 125°C ⁇ 126°C ⁇ 127°C ⁇ 128°C ⁇ 129°C ⁇ 130°C ,Wait.
- the drying temperature is 100°C.
- the drying time is 8-80min, for example: 8min, 9min, 10min, 12min, 15min, 16min, 18min, 20min, 22min, 24min, 25min, 27min, 28min, 29min, 30min, 32min, 34min, 35min, 38min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 78min, 80min, etc.
- the drying time is 27-30min, for example: 27min, 28min, 29min, 30min, etc.
- the thickness of the graphene oxide film is 50-500 ⁇ m, for example: 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 120 ⁇ m, 150 ⁇ m, 180 ⁇ m, 200 ⁇ m, 220 ⁇ m, 250 ⁇ m, 280 ⁇ m, 300 ⁇ m, 320 ⁇ m, 350 ⁇ m, 380 ⁇ m, 400 ⁇ m, 420 ⁇ m , 450 ⁇ m, 480 ⁇ m, 490 ⁇ m, 500 ⁇ m, etc.
- the thickness of the graphene oxide film is 200 ⁇ m.
- a graphene thermally conductive film is shown.
- the thermal conductivity of the graphene thermally conductive film is 1000-1600W/m ⁇ k, for example: 1000W/m ⁇ k, 1100W/m ⁇ k, 1200W /m ⁇ k, 1300W/m ⁇ k, 1400W/m ⁇ k, 1500W/m ⁇ k, 1600W/m ⁇ k, etc.
- the thermal conductivity of the graphene thermally conductive film is 1500 W/m ⁇ k.
- the density of the graphene thermal film is 1.5-2.2g/cm 3 , for example: 1.5g/cm 3 , 1.6g/cm 3 , 1.7g/cm 3 , 1.8g/cm 3 , 1.9g/cm 3 , 2.0g/ m 3 , 2.1g/cm 3 , 2.2g/cm 3 , 2.2g/cm 3 , etc.
- the density of the graphene thermally conductive film is 2.0 g/m 3 .
- the thickness of the graphene thermally conductive film is 10-150 ⁇ m, for example: 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 140 ⁇ m, 150 ⁇ m, etc.
- the thickness of the ink thermal conductive film is 40 ⁇ m.
- the graphene oxide film is prepared by the method of the fourth embodiment of the present invention, which is heat-treated and calendered to obtain a graphene thermally conductive film.
- the specific preparation process is shown in Figure 5.
- the graphene oxide filter cake prepared by the Hummers method is first mixed with a solvent, stirred and dispersed to obtain a graphene oxide slurry; then the graphene oxide slurry is ultra-fine to reduce the viscosity to obtain Low-viscosity graphene oxide slurry; then the low-viscosity graphene oxide slurry is defoamed, coated on the substrate, dried, and peeled to obtain a graphene oxide film; then the graphene oxide film is heat-treated to obtain graphite Foam film; Finally, the graphene foam film is calendered to obtain a graphene thermal film.
- the solid content of the graphene oxide slurry is 5-10%, which improves coating efficiency.
- the appearance, density, thermal conductivity, cohesion, tensile strength, etc. of the graphene thermally conductive film are equivalent to those of graphene thermally conductive film prepared from graphene oxide slurry with a solid content of 2-4% that have not passed the viscosity reduction treatment. The efficiency is higher.
- the heat treatment temperature is 1000-3000°C, for example: 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, 1600°C, 1700°C, 1800°C, 1900°C, 2000°C, 2100°C, 2200°C, 2300°C, 2400°C, 2500°C, 2600°C, 2700°C, 2800°C, 2900°C, 3000°C, etc.
- the temperature of the heat treatment is 2000°C.
- the density of the graphene oxide film after heat treatment is 0.1-1.0g/cm 3 , for example: 0.1g/cm 3 , 0.2g/cm 3 , 0.3g/cm 3 , 0.4g/cm 3 , 0.5g/cm 3 , 0.6 g/cm 3 , 0.7g/cm 3 , 0.8g/cm 3 , 0.9g/cm 3 , 1.0g/cm 3 , etc.
- the density of the graphene oxide film after heat treatment is 0.3 g/cm 3 .
- the calendering pressure is 50-200t, for example: 50t, 60t, 70t, 80t, 90t, 100t, 110t, 120t, 130t, 140t, 150t, 160t, 170t, 180t, 190t, 200t, etc.
- the calendering pressure is 100t.
- Step 1) Use a dispersion device to disperse the graphene oxide filter cake with a solid content of 5.0% in deionized water at a linear velocity of 5 m/s, and the viscosity of the graphene oxide slurry obtained after dispersion for 2 hours is 100000 mPa ⁇ s;
- Step 2) Ultrafine the graphene oxide slurry with a pressure of 50 MPa, and the obtained low-viscosity graphene oxide slurry has a viscosity of 20000 mPa ⁇ s;
- Step 3) Use a degassing device to vacuum degas the low viscosity graphene oxide slurry of step 2), and the vacuum value is -80kPa;
- Step 4) Use a doctor blade coating method to coat the degassed slurry in step 3) on the PET film, and dry it at 80°C for 75 minutes to obtain the graphene oxide film directly peeled and wound, and the coating thickness is 2.5mm , The coating speed is 1.2m/min;
- Step 5) slitting the graphene oxide film roll material obtained in step 4) winding, as shown in Figure 6, to obtain a graphene oxide film with a size of 300mm*300mm;
- Step 6) Perform a high temperature heat treatment at 2000°C on the graphene oxide film obtained in step 5) to obtain a graphene foam film with a density of 0.3 g/cm 3;
- Step 7) Use a pressure of 100t to calender the graphene foam film of step 6), as shown in Figure 7, to obtain a graphene with a density of 2.0 g/cm 3 , a thickness of 40 ⁇ m, and a thermal conductivity of 1500 W/m ⁇ K Thermally conductive film.
- Step 1) Use a dispersion device to disperse the graphene oxide filter cake with a solid content of 10.0% in deionized water at a linear velocity of 5 m/s, and the viscosity of the graphene oxide slurry obtained after dispersion for 2 hours is 200,000 mPa ⁇ s;
- Step 2) Ultrafine the graphene oxide slurry, the pressure is 100 MPa, and the obtained low-viscosity graphene oxide slurry has a viscosity of 20000 mPa ⁇ s;
- Step 3) Use a degassing device to vacuum degas the low viscosity graphene oxide slurry of step 2), and the vacuum value is -80kPa;
- Step 4) Use a doctor blade coating method to coat the degassed slurry in step 3) on the PET film, and dry it at 120°C for 11 minutes to obtain the graphene oxide film directly peeled and wound, and the coating thickness is 0.75mm , The coating speed is 8.0m/min;
- Step 5) slitting the graphene oxide film roll material obtained in step 4) winding, as shown in Figure 8, to obtain a graphene oxide film with a size of 300mm*300mm;
- Step 6) Perform a high temperature heat treatment at 2000°C on the graphene oxide film obtained in step 5) to obtain a graphene foam film with a density of 0.3 g/cm 3;
- Step 7) Use a pressure of 100t to calender the graphene foam film of step 6) to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thickness of 20 ⁇ m, and a thermal conductivity of 1500 W/m ⁇ K.
- Step 1) Use a dispersion device to disperse the graphene oxide filter cake with a solid content of 8.0% in deionized water at a linear velocity of 5 m/s, and the viscosity of the graphene oxide slurry obtained after dispersion for 2 hours is 150,000 mPa ⁇ s;
- Step 2) Ultrafine the graphene oxide slurry, the pressure is 100 MPa, and the obtained low-viscosity graphene oxide slurry has a viscosity of 20000 mPa ⁇ s;
- Step 3) Use a degassing device to vacuum degas the low viscosity graphene oxide slurry of step 2), and the vacuum value is -80kPa;
- Step 4) Use a doctor blade coating method to coat the degassed slurry of step 3) on the PET film, and dry it at 100°C for 30 minutes to obtain the graphene oxide film directly peeled and wound, and the coating thickness is 1.5mm , The coating speed is 3m/min;
- Step 5) slitting the graphene oxide film roll obtained in step 4), as shown in FIG. 9, to obtain a graphene oxide film with a size of 300mm*300mm;
- Step 6) Perform a high temperature heat treatment at 2000°C on the graphene oxide film obtained in step 5) to obtain a graphene foam film with a density of 0.3 g/cm 3;
- Step 7) calender the graphene foam film of step 6) with a pressure of 100 t to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thickness of 40 ⁇ m, and a thermal conductivity of 1500 W/m ⁇ K.
- Step 1) Use a dispersion device to disperse the graphene oxide filter cake with a solid content of 2.0% in deionized water at a linear velocity of 2m/s, and the viscosity of the graphene oxide slurry obtained after dispersion for 2h is 20000mPa ⁇ s;
- Step 2) Use a degassing device to vacuum degas the graphene oxide slurry of step 1), and the vacuum value is -80kPa;
- Step 3) Use a doctor blade coating method to coat the degassed slurry in step 2) on a PET film, and dry it at 70°C for 5 hours to obtain a graphene oxide film that is directly peeled and wound, and the coating thickness is 6.0mm , The coating speed is 0.3m/min;
- Step 4) slitting the graphene oxide film roll obtained in step 3) to obtain a graphene oxide film with a size of 300mm*300mm;
- Step 5) Perform a high temperature heat treatment at 2000°C on the graphene oxide film obtained in step 4) to obtain a graphene foam film with a density of 0.3 g/cm 3;
- Step 6) Use a pressure of 100t to calender the graphene foam film of step 5) to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thickness of 40 ⁇ m, and a thermal conductivity of 1500 W/m ⁇ K.
- Step 1) Use a dispersion device to disperse the graphene oxide filter cake with a solid content of 8.0% in deionized water at a linear velocity of 5 m/s, and the viscosity of the graphene oxide slurry obtained after dispersion for 2 hours is 150,000 mPa ⁇ s;
- Step 2) Use a degassing device to vacuum degas the graphene oxide slurry of step 1).
- the existing degassing technology cannot completely remove the bubbles in the slurry;
- Step 3) Use a doctor blade coating method to coat the degassed slurry in step 2) on a PET film, and dry it at 100°C to obtain a graphene oxide film that is directly peeled and wound, and the coating thickness is 1.5mm.
- the coating speed is 3m/min, as shown in Figure 10, the appearance of the dried graphene oxide film has defects;
- Step 4) slitting the graphene oxide film roll obtained in step 3) to obtain a graphene oxide film with a size of 300mm*300mm;
- Step 5) Perform a high temperature heat treatment at 2000°C on the graphene oxide film obtained in step 4) to obtain a graphene foam film with a density of 0.3 g/cm 3;
- Step 6) Use a pressure of 100t to calender the graphene foam film of step 5) to obtain a graphene thermal conductive film with a density of 2.0 g/cm 3 , a thickness of 40 ⁇ m, and a thermal conductivity of 900 W/m ⁇ K, as shown in Figure 11 As shown, the appearance of the thermally conductive film is defective.
- the ultra-micronization method of the present invention can reduce the viscosity of the graphene oxide slurry and increase the solid content, thereby achieving the following effects:
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Abstract
Description
Claims (10)
- 一种低粘度的氧化石墨烯浆料,其特征在于,所述氧化石墨烯浆料的固含量为5-10%;优选地,所述氧化石墨烯浆料的粘度为10000-50000mPa·s。
- 根据权利要求1所述的低粘度的氧化石墨烯浆料,其特征在于,所述氧化石墨烯浆料的粘度为20000mPa·s;优选地,所述氧化石墨烯浆料的固含量为8%;优选地,所述低粘度的氧化石墨烯浆料中为氧化石墨烯微片,平均片径为2-3μm。
- 一种低粘度的氧化石墨烯浆料的制备方法,其特征在于,将氧化石墨烯与溶剂混合,分散,超微细化使氧化石墨烯的平均片径减小,得到低粘度的氧化石墨烯浆料。
- 根据权利要求3所述的低粘度的氧化石墨烯浆料的制备方法,其特征在于,所述氧化石墨烯通过Hummers法制备得到;优选地,所述氧化石墨烯中,氧和碳的摩尔比为0.6-0.7,优选0.65;优选地,所述溶剂为水;优选地,所述分散的线速度为2-20m/s,优选5m/s;优选地,所述分散的时间为1-5h,优选2h;优选地,所述超微细化的方法包括对氧化石墨烯与溶剂的混合物施加压力,使混合物通过狭缝,在通过狭缝的过程中受到高压剪切和高速撞击,并在通过狭缝后,由于压力能的瞬间释放而产生强烈的空穴作用;优选地,施加的压力为50-250MPa,优选100MPa;优选地,超微细化至氧化石墨烯的平均片径为2-3μm;优选地,所述氧化石墨烯浆料在超微细化前的粘度为100000-200000mPa·s;优选地,所述氧化石墨烯浆料在超微细化后的粘度为10000-50000mPa·s,优选20000mPa·s;优选地,所述氧化石墨烯浆料的固含量为5-10%,优选8%。
- 一种氧化石墨烯膜,其特征在于,所述氧化石墨烯膜中的氧化石墨烯的平均片径为2-3μm。
- 根据权利要求5所述的氧化石墨烯膜,其特征在于,所述氧化石墨烯膜的厚度为50-500μm,优选200μm;优选地,所述氧化石墨烯膜的密度为1.0-2.0g/cm 3,优选1.5g/cm 3。
- 一种氧化石墨烯膜的制备方法,其特征在于,采用权利要求3-5中任一项的方法制备低粘度的氧化石墨烯浆料,经脱泡处理后,再将脱泡的氧化石墨烯浆料涂布到基底表面,经干燥,剥离,得到氧化石墨烯膜。
- 根据权利要求7所述的氧化石墨烯膜的制备方法,其特征在于,所述脱泡为真空脱泡,所述真空脱泡的真空值为-95至-50kPa,优选-80kPa;优选地,所述脱泡采用在线式连续脱泡机;优选地,所述涂布采用刮刀涂布或挤出涂布的方式,所述涂布的速度为1-10m/min,优选3m/min;优选地,所述涂布的厚度为0.5-5.0mm,优选1.5mm;优选地,所述干燥的温度为70-130℃,优选100℃;优选地,所述干燥的时间为8-80min,优选27-30min;优选地,所述氧化石墨烯膜的厚度为50-500μm,优选200μm。
- 一种石墨烯导热膜,其特征在于,所述石墨烯导热膜的导热系数为1000-1600W/m·K,优选1500W/m·K;优选地,所述石墨烯导热膜的密度为1.5-2.2g/cm 3,优选2.0g/cm 3;优选地,所述石墨烯导热膜的厚度为10-150μm,优选40μm。
- 一种石墨烯导热膜的制备方法,其特征在于,采用权利要求7或8的方法制备氧化石墨烯膜,经热处理,压延,得到石墨烯导热膜;优选地,所述热处理的温度为1000-3000℃,优选2000℃;优选地,所述氧化石墨烯膜热处理后的密度为0.1-1.0g/cm 3,优选0.3g/cm 3;优选地,所述压延的压力为50-200t,优选100t。
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CN112408385B (zh) | 2021-08-27 |
CN113479875B (zh) | 2022-08-12 |
EP4019467A1 (en) | 2022-06-29 |
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CN112408385A (zh) | 2021-02-26 |
EP4019467A4 (en) | 2022-10-26 |
CN113511652A (zh) | 2021-10-19 |
KR20220051353A (ko) | 2022-04-26 |
KR102514129B1 (ko) | 2023-03-24 |
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JP7273247B2 (ja) | 2023-05-12 |
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US20220267156A1 (en) | 2022-08-25 |
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CN113511652B (zh) | 2022-08-19 |
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