WO2021043030A1 - 强、弱氧化石墨烯的混合浆料及其制备方法、强、弱氧化石墨烯的复合膜及其制备方法 - Google Patents

强、弱氧化石墨烯的混合浆料及其制备方法、强、弱氧化石墨烯的复合膜及其制备方法 Download PDF

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WO2021043030A1
WO2021043030A1 PCT/CN2020/111173 CN2020111173W WO2021043030A1 WO 2021043030 A1 WO2021043030 A1 WO 2021043030A1 CN 2020111173 W CN2020111173 W CN 2020111173W WO 2021043030 A1 WO2021043030 A1 WO 2021043030A1
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graphene oxide
strong
weak
graphene
film
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PCT/CN2020/111173
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English (en)
French (fr)
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周步存
周仁杰
卢静
苏冬
王兆成
李峰
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常州富烯科技股份有限公司
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Priority to EP20861345.5A priority Critical patent/EP4019466A4/en
Priority to JP2022514771A priority patent/JP7274046B2/ja
Priority to KR1020227008095A priority patent/KR102461402B1/ko
Priority to US17/753,531 priority patent/US11518678B2/en
Publication of WO2021043030A1 publication Critical patent/WO2021043030A1/zh
Priority to US17/653,755 priority patent/US11618682B2/en

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    • C01B32/00—Carbon; Compounds thereof
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    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the invention relates to the field of materials, in particular to a process for preparing a graphene thermal conductive film by using graphene oxide.
  • Graphene has good thermal conductivity and has a wide range of application prospects.
  • the graphene oxide film is arranged and assembled into a graphene oxide film, and then subjected to high temperature treatment to prepare a graphene thermal conductive film is a commonly used process for preparing a graphene thermal conductive film.
  • the graphene thermally conductive film prepared by this method is a highly oriented thermally conductive film formed by stacking multiple layers of graphene. It has the characteristics of good mechanical properties, high thermal conductivity, light weight, thin materials, and good flexibility. It can solve electronic problems. , Aerospace, medical and other industries.
  • the graphene oxide used in the prior art is graphene oxide obtained by chemically oxidizing graphite, which has abundant oxygen-containing functional groups, and generally has a carbon content of about 50%.
  • the arrangement and assembly performance of this graphene oxide is good, but the graphene thermal conductive film is prepared by using the graphene oxide, and the final thermal conductive film obtained per unit mass of graphene oxide has less carbon, which increases the cost and is not conducive to industrial production.
  • the content of the background technology is only the technology known to the inventor, and does not of course represent the existing technology in this field.
  • the present invention provides a graphene oxide slurry.
  • the slurry includes two graphene oxides with different oxidation degrees, which can increase the carbon content per unit mass of graphene oxide. , So that the resulting graphene thermal conductive film has more carbon.
  • the present invention provides a strong and weak graphene oxide mixed slurry, which includes graphene oxide and a solvent, and the graphene oxide includes strong graphene oxide and weak graphene oxide.
  • the strong graphene oxide in the present invention refers to graphene oxide with a strong degree of oxidation
  • weak graphene oxide refers to graphene oxide with a weak degree of oxidation
  • Graphene oxide is obtained by adding some substances and structures between the layers of graphite to peel off the graphite flakes. Only after reaching a certain degree of intercalation and oxidation can it be stripped to obtain very thin flakes (3 layers and the following). Graphene oxide has a high degree of oxidation, more oxygen-containing functional groups, thinner lamellae, more orderly in the assembly into a film, and better assembly effect, but the carbon content of strong graphene oxide is low, and the graphite obtained after high temperature treatment The amount of olefin is less.
  • the carbon content of weak graphene oxide is high, and the amount of graphene obtained after high temperature treatment is more, but the weaker degree of oxidation only oxidizes at the edge of the graphite sheet, and it is impossible to obtain graphene oxide with a small number of sheets through exfoliation. It is also almost difficult to prepare graphene oxide with weak oxidation and thin peeling layers through experiments.
  • the degree of oxidation of weak graphene oxide is low, the number of oxygen-containing functional groups is small, and the number of layers is large during exfoliation. If only weak graphene oxide is used to assemble the film, a highly oriented structure will not be obtained during film formation, and the orderliness is not good. Affect the improvement of the thermal conductivity of the graphene thermally conductive film obtained after high temperature treatment.
  • the present invention provides a mixed slurry of strong and weak graphene oxide. Under the condition that the order of the assembled film is not greatly affected, the amount of graphene thermally conductive film after high-temperature treatment is large and the thermal conductivity of the graphene thermally conductive film is increased. The performance is good.
  • the solid content of the graphene oxide is 5-8%.
  • the weak graphene oxide accounts for 5-50% of the mass of the graphene oxide, preferably 5-30%, more preferably 10-30%.
  • the carbon content of the strong graphene oxide is 45-55%.
  • the carbon content of the weak graphene oxide is 80-90%.
  • the carbon content of the weak graphene oxide is selected in the range of 80-90% because the graphene oxide with too high carbon content has a higher number of layers when it is peeled off, and the orderliness of assembly will be worse.
  • the solvent includes one or a mixed solvent of more than one of water, NMP, and DMF.
  • two graphene oxides with different oxidation levels are mixed in a solvent, because the surface of both graphene oxides contains hydrophilic oxygen-containing functional groups, and both have Negative charges, repel each other in the solvent, are not easy to agglomerate, and have good mutual dispersion properties.
  • the present invention also provides a method for preparing a mixed slurry of strong and weak graphene oxide, which specifically includes the following steps:
  • the strong graphene oxide dispersion liquid and the weak graphene oxide dispersion liquid are respectively prepared, and the strong graphene oxide dispersion liquid and the weak graphene oxide dispersion liquid are mixed and dispersed to obtain a mixed slurry of strong and weak graphene oxide.
  • the two graphene oxides are directly mixed and then the alkali is added, because the oxidation degree of the two graphene oxides is different, the amount of -COOH contained in the structure is different.
  • the reaction will be uneven, resulting in uneven dispersion.
  • the two graphene oxides are first dispersed well, and the -COOH groups on the graphene oxide are fully neutralized, and then the two are mixed to avoid the above-mentioned uneven dispersion problem. Therefore, first disperse the two graphene oxides in the solvent separately to fully neutralize the -COOH of the graphene oxide, and then mix the two to make the two graphene oxides in the mixed solution not easy to agglomerate.
  • a method for preparing a strong graphene oxide dispersion includes: dispersing graphene oxide prepared by a chemical oxidation method in a solvent to obtain a strong graphene oxide dispersion.
  • the chemical oxidation method is to react graphite with an oxidant in a strong acid solution to obtain graphene oxide.
  • the chemical oxidation method includes Bordie method, Staudenmaier method and Hummers method.
  • the solid content of the strong graphene oxide is 3-8%.
  • the solid content of the weak graphene oxide is 7-11%.
  • weak graphene oxide contains less oxygen-containing functional groups and less solvents, it is easier to obtain a high-concentration slurry; because the number of layers of weak graphene oxide exfoliated is not as small as that of strong graphene oxide. Therefore, a dispersion of weak graphene oxide with a higher solid content can be obtained.
  • high-speed dispersion is adopted for the mixture of the strong graphene oxide dispersion and the weak graphene oxide dispersion, and the linear velocity of the dispersion is 50-300 m/s, preferably 100 m/s.
  • the present invention also provides a composite film of strong and weak graphene oxide, including strong graphene oxide and weak graphene oxide, the content of the weak graphene oxide is 5-50%, preferably 5-30%, more preferably 10 -30%.
  • the strong graphene oxide has a better degree of exfoliation, it can help the weak graphene oxide to be assembled in an orderly manner. Due to the high carbon content of the weak graphene oxide, the graphene thermal conductive film prepared from the graphene oxide composite film per unit mass increases. , Saving costs.
  • the final graphene thermally conductive film has high thermal conductivity, but the thickness of the graphene thermally conductive film is thin; if only weak graphene oxide is used to prepare graphene thermally conductive film, or weakly oxidized The content of graphene is too much, because the weakly oxidized graphene oxide is difficult to peel off to obtain graphene oxide with few layers (less than 10 layers), and the ordering during assembly is not good.
  • the thermal conductivity of the graphene thermal film after the final heat treatment Low; if only graphene oxide with a middle degree of oxidation is used, the degree of oxidation is lower than that of strong graphene oxide.
  • the grammage of the graphene oxide composite film is 100-250 g/m 2 , preferably 180 g/m 2 .
  • the carbon content of the strong graphene oxide is 45-55%.
  • the carbon content of the weak graphene oxide is 80-90%.
  • the strong graphene oxide and the weak graphene oxide of the composite film are aligned in-plane.
  • In-plane oriented arrangement refers to that graphene oxide is assembled into a film through hydrogen bonds, and is oriented in the assembled plane, so that the heat of the heat-treated graphene thermally conductive film can be transferred along the direction of the oriented arrangement of graphene.
  • the present invention also provides a method for preparing a composite film of strong and weak graphene oxide, which specifically includes the following steps:
  • the slurry is defoamed, coated, and dried to form a composite film of strong and weak graphene oxide.
  • a continuous on-line deaeration machine is used for defoaming, and the rotation speed is 2000-3000 r/min.
  • the opening of the feed valve of the deaerator is 25-35%, preferably 30%.
  • the vacuum negative pressure in the deaerator is 400-600Pa, preferably 500Pa.
  • the coating method includes blade coating and slit extrusion coating, preferably blade coating, and further preferably using a coater for blade coating.
  • the method of slit extrusion coating is to let a certain flow of slurry enter the die's internal cavity from the feed port of the extrusion head, and form a stable pressure.
  • the slurry is finally sprayed out at the die slit outlet and coated on the substrate. Material.
  • Blade coating is a coating method in which a doctor blade is used for coating to produce a thick coating film.
  • the thickness of the wet film formed by coating is 2-5 mm, preferably 3 mm. Because the carbon content of weak graphene oxide is high, the carbon residual value of the final thermal conductive film can be increased, so that a thicker graphene thermal conductive film can be obtained with the same thickness of the graphene oxide coating. If it is necessary to prepare a graphene thermally conductive film of the same thickness, the method of the present invention can make the thickness of the wet film formed by coating thinner, which can greatly reduce the film production cost and improve the efficiency.
  • the coating speed is 1-2 m/min, preferably 1.2 m/min.
  • the drying temperature is 50-100°C, and the drying time is 0.5-1.5h.
  • the present invention also provides a graphene thermally conductive film, the thermal conductivity of the graphene thermally conductive film is greater than 1000 W/m ⁇ K.
  • the density of the graphene thermally conductive film is 1.9-2.1 g/cm 3 .
  • the thickness of the graphene thermally conductive film is 30-100 ⁇ m.
  • the present invention also provides a method for preparing a graphene thermally conductive film, which includes the following steps:
  • the composite film after high temperature treatment is compacted to obtain a graphene thermal conductive film.
  • the graphene oxide composite film has a higher carbon content, the amount of the graphene thermally conductive film that is too thick after high temperature treatment is large, which can greatly reduce the film production cost and improve the efficiency.
  • the method for high-temperature treatment of the composite membrane includes: heating the composite membrane from room temperature to 1000-3000° C., and treating for 5-15 hours.
  • the heating rate is 0.2-5°C/min.
  • the heating rate when the temperature is below 100°C, the heating rate is 1-1.5°C/min, when it is greater than 100°C and below 300°C, the heating rate is 0.2-0.5°C/min, and when it is greater than 300°C, the heating rate is 3-5°C/min. °C/min.
  • the pressure of compaction is 10-30 MPa.
  • two graphene oxides of different degrees are mixed to prepare graphene thermal conductive film.
  • the graphene oxide with strong oxidation degree is rich in functional groups, the assembly order is good, and the graphene oxide with weak oxidation degree has high carbon content, so that the prepared graphene oxide
  • the graphene thermal conductive film is thicker, and the final residual carbon ratio is increased, which can improve production efficiency and effectively reduce costs.
  • the slurry of the present invention only needs to coat a 2mm wet film to obtain a 32 ⁇ m graphene thermal conductivity.
  • the graphene oxide slurry with a strong degree of oxidation needs to be coated with a 4.5mm wet film to obtain a 31 ⁇ m graphene thermal film; the graphene oxide slurry with a strong degree of oxidation and a mixed slurry of strong and weak graphene oxide Coating 4.5mm wet film respectively, the graphene oxide slurry with strong oxidation degree finally obtains a 31 ⁇ m graphene thermal conductive film, and the mixed slurry of strong and weak graphene oxide finally obtains a 72 ⁇ m graphene thermal conductive film.
  • FIG. 1 is an SEM image of the graphene oxide film of Example 1;
  • FIG. 5 is an SEM image of the graphene oxide film of Comparative Example 5.
  • a mixed slurry of strong and weak graphene oxide including graphene oxide and a solvent, and the graphene oxide includes strong graphene oxide and weak graphene oxide.
  • the solid content of graphene oxide is 5-8%, for example: 5%, 5.2%, 5.4%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, etc.
  • Weak graphene oxide accounts for 5-50% of the mass of graphene oxide, for example: 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 42%, 45%, 48%, 49%, 50%, etc.
  • the carbon content of strong graphene oxide is 45-55%, for example: 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, etc.
  • the carbon content of weak graphene oxide is 80-90%, for example: 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, etc.
  • weak graphene oxide accounts for 5-30% of the mass of graphene oxide, for example: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 19%, 20%, 22%, 25%, 28%, 29%, 30%, etc.
  • weak graphene oxide accounts for 10-30% of the mass of graphene oxide, for example: 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% , 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.
  • the carbon content of the weak graphene oxide is selected in the range of 80-90% because the graphene oxide with too high carbon content has a higher number of layers when it is peeled off, and the orderliness of assembly will be worse.
  • the solvent includes one or a mixed solvent of two or more of water, NMP, and DMF.
  • the strong graphene oxide in the present invention refers to graphene oxide with a strong degree of oxidation
  • weak graphene oxide refers to graphene oxide with a weak degree of oxidation
  • Graphene oxide is obtained by adding some substances and structures between the layers of graphite to peel off the graphite flakes. Only after reaching a certain degree of intercalation and oxidation can it be stripped to obtain very thin flakes (3 layers and the following). Graphene oxide has a high degree of oxidation, more oxygen-containing functional groups, thinner lamellae, more orderly in the assembly into a film, and better assembly effect, but the carbon content of strong graphene oxide is low, and the graphite obtained after high temperature treatment The amount of olefin is less.
  • the carbon content of weak graphene oxide is high, and the amount of graphene obtained after high temperature treatment is more, but the weaker degree of oxidation only oxidizes at the edge of the graphite sheet, and it is impossible to obtain graphene oxide with a small number of sheets through exfoliation. It is also almost difficult to prepare graphene oxide with weak oxidation and thin peeling layers through experiments.
  • the degree of oxidation of weak graphene oxide is less oxygen-containing functional groups, and there are more layers during peeling. If only weak graphene oxide is used to assemble the film, a highly oriented structure will not be obtained during film formation, and the orderliness is not good. Affect the improvement of the thermal conductivity of the graphene thermally conductive film obtained after high temperature treatment.
  • the strong graphene oxide dispersion liquid and the weak graphene oxide dispersion liquid are respectively prepared, and the strong graphene oxide dispersion liquid and the weak graphene oxide dispersion liquid are mixed and dispersed to obtain a mixed slurry of strong and weak graphene oxide.
  • the two graphene oxides are directly mixed and then the alkali is added, because the oxidation degree of the two graphene oxides is different, the amount of -COOH contained in the structure is different.
  • the reaction will be uneven, resulting in uneven dispersion.
  • the two graphene oxides are first dispersed well, and the -COOH groups on the graphene oxide are fully neutralized, and then the two are mixed to avoid the above-mentioned uneven dispersion problem. Therefore, first disperse the two graphene oxides in the solvent separately to fully neutralize the -COOH of the graphene oxide, and then mix the two to make the two graphene oxides in the mixed solution not easy to agglomerate.
  • the preparation method of the strong graphene oxide dispersion liquid includes: dispersing the graphene oxide prepared by the chemical oxidation method in a solvent to obtain the strong graphene oxide dispersion liquid.
  • the chemical oxidation method is to react graphite with an oxidant in a strong acid solution to obtain graphene oxide.
  • Chemical oxidation methods include Bordie method, Staudenmaier method and Hummers method.
  • the solid content of strong graphene oxide is 3-8%, for example: 3%, 4%, 5%, 6%, 7%, 8%, etc.
  • the solid content of the weak graphene oxide is 7-11%, for example: 7%, 8%, 9%, 10%, 11%, etc. Because weak graphene oxide contains less oxygen-containing functional groups and less solvents, it is easier to obtain a high-concentration slurry; because the number of layers of weak graphene oxide exfoliated is not as small as that of strong graphene oxide. Therefore, a dispersion of weak graphene oxide with a higher solid content can be obtained.
  • High-speed dispersion is used for the mixture of strong graphene oxide dispersion and weak graphene oxide dispersion.
  • the linear velocity of dispersion is 50-300m/s, for example: 50m/s, 60m/s, 70m/s, 80m/s, 90m/s, 100m/s, 120m/s, 150m/s, 180m/s, 200m/s, 220m/s, 240m/s, 250m/s, 280m/s, 290m/s, 300m/s, etc.
  • the linear velocity of dispersion is 100 m/s.
  • a composite film of weak and weak graphene oxide including strong graphene oxide and weak graphene oxide, and the content of weak graphene oxide is 5-50%, for example: 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 42%, 45%, 48%, 49%, 50% ,Wait.
  • the content of weak graphene oxide is 5-30%, for example: 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 18%, 19%, 20%, 21%, 24%, 25%, 28%, 29%, 30%, etc.
  • the content of weak graphene oxide is 10-30%, for example: 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% , 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.
  • the strong graphene oxide has a better degree of exfoliation, it can help the weak graphene oxide to be assembled in an orderly manner. Due to the high carbon content of the weak graphene oxide, the graphene thermal conductive film prepared from the graphene oxide composite film per unit mass increases. , Saving costs.
  • the final graphene thermally conductive film has high thermal conductivity, but the thickness of the graphene thermally conductive film is thin; if only weak graphene oxide is used to prepare graphene thermally conductive film, or weakly oxidized The content of graphene is too much, because the weakly oxidized graphene oxide is difficult to peel off to obtain graphene oxide with few layers (less than 10 layers), and the ordering during assembly is not good.
  • the thermal conductivity of the graphene thermal film after the final heat treatment Low; if only graphene oxide with a middle degree of oxidation is used, the degree of oxidation is lower than that of strong graphene oxide.
  • the weight of the graphene oxide composite film is 100-250g/m 2 , for example: 100g/m 2 , 110g/m 2 , 120g/m 2 , 140g/m 2 , 150g/m 2 , 180g/m 2 , 200g/ m 2 , 220g/m 2 , 230g/m 2 , 240g/m 2 , 250g/m 2 , etc.
  • the grammage of the graphene oxide composite film is 180 g/m 2 .
  • the carbon content of strong graphene oxide is 45-55%, for example: 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, etc.
  • the carbon content of weak graphene oxide is 80-90%, for example: 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, etc.
  • the strong graphene oxide and weak graphene oxide of the graphene oxide composite film are aligned in-plane.
  • In-plane oriented arrangement refers to that graphene oxide is assembled into a film through hydrogen bonding, and is oriented in the assembled plane, so that the heat of the heat-treated graphene thermally conductive film can be transmitted along the direction of the oriented arrangement of graphene.
  • a method for preparing a composite film of strong and weak graphene oxide is shown, which specifically includes the following steps:
  • the slurry is defoamed, coated, and dried to form a composite film of strong and weak graphene oxide.
  • Deaeration adopts continuous online deaeration machine, the speed is 2000-3000r/min, for example: 2000r/min, 2100r/min, 2200r/min, 2300r/min, 2400r/min, 2500r/min, 2600r/min, 2700r/min , 2800r/min, 2900r/min, 3000r/min, etc.
  • the opening of the feed valve of the deaerator is 25-35%, for example: 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, Wait.
  • the opening degree of the feed valve of the deaerator is 30%.
  • the vacuum negative pressure in the deaerator is 400-600Pa, for example: 400Pa, 420Pa, 440Pa, 450Pa, 480Pa, 490Pa, 500Pa, 520Pa, 550Pa, 580Pa, 590Pa, 600Pa, etc.
  • the vacuum negative pressure in the deaerator is 500Pa.
  • Coating methods include slit extrusion coating and knife coating. The method of slit extrusion coating is to let a certain flow of slurry enter the die's internal cavity from the feed port of the extrusion head, and form a stable pressure. The slurry is finally sprayed out at the die slit outlet and coated on the substrate. Material.
  • Blade coating is a coating method in which a doctor blade is used for coating to produce a thick coating film. It is preferable to use a blade coating method, and it is more preferable to use a coater for blade coating.
  • the thickness of the wet film formed by coating is 2-5mm, for example: 2mm, 2.2mm, 2.5mm, 2.8mm, 3mm, 3.2mm, 3.5mm, 3.8mm, 4mm, 4.2mm, 4.5mm, 4.8mm, 5mm, etc. .
  • the thickness of the wet film formed by coating is 3 mm.
  • the method of the present invention can make the thickness of the wet film formed by coating thinner, which can greatly reduce the film production cost and improve the efficiency.
  • the coating speed is 1-2m/min, for example: 1m/min, 1.1m/min, 1.2m/min, 1.3m/min, 1.4m/min, 1.5m/min, 1.6m/min, 1.7m/ min, 1.8m/min, 1.9m/min, 2m/min, etc.
  • the coating speed is 1.2 m/min.
  • the drying temperature is 50-100°C, for example: 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, etc.; the drying time is 0.5-1.5h, for example: 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, etc.
  • a graphene thermally conductive film is shown, the thermal conductivity of the graphene thermally conductive film is greater than 1000W/m ⁇ K, for example: 1100W/m ⁇ K, 1200W/m ⁇ K, 1300W /m ⁇ K, 1400W/m ⁇ K, 1500W/m ⁇ K, 1600W/m ⁇ K, 1700W/m ⁇ K, 1800W/m ⁇ K, etc.
  • the density of the thermally conductive graphene film is 1.9-2.1g / cm 3, for example: 1.9g / cm 3, 1.92g / cm 3, 19.5g / cm 3, 19.8g / cm 3, 2.0g / cm 3, 2.02g / cm 3 , 2.05g/cm 3 , 2.08g/cm 3 , 2.1g/cm 3 , etc.
  • the thickness of the graphene thermally conductive film is 30-100 ⁇ m, for example: 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 85 ⁇ m, 90 ⁇ m, 95 ⁇ m, 100 ⁇ m, etc.
  • a method for preparing a graphene thermally conductive film which includes the following steps:
  • the method of the fourth embodiment is used to prepare a composite film of strong and weak graphene oxide
  • the composite film after high temperature treatment is compacted to obtain a graphene thermal conductive film.
  • the graphene oxide composite film has a higher carbon content, the amount of the graphene thermally conductive film that is too thick after high temperature treatment is large, which can greatly reduce the film production cost and improve the efficiency.
  • the method of high-temperature treatment of the composite membrane includes: heating the composite membrane from room temperature to 1000-3000°C, for example: 1000°C, 1200°C, 1500°C, 1800°C, 2000°C, 2200°C, 2500°C, 2800°C, 3000°C , Etc.; process 5-15h, for example: 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, etc.
  • the heating rate is 0.2-5°C/min, for example: 0.2°C/min, 0.3°C/min, 0.4°C/min, 0.5°C/min, 0.8°C/min, 1°C/min, 1.5°C/min, 2°C/ min, 2.5°C/min, 3°C/min, 3.5°C/min, 4°C/min, 4.5°C/min, 4.8°C/min, 4.9°C/min, 5°C/min, etc.
  • the heating rate when the temperature is below 100°C, the heating rate is 1-1.5°C/min, for example: 1°C/min, 1.1°C/min, 1.2°C/min, 1.3°C/min, 1.4°C/min, 1.5°C /min, etc.; when greater than 100°C and below 300°C, the heating rate is 0.2-0.5°C/min, for example: 0.2°C/min, 0.3°C/min, 0.4°C/min, 0.5°C/min, etc.; greater than At 300°C, the heating rate is 3-5°C/min, for example: 3°C/min, 3.2°C/min, 3.5°C/min, 3.8°C/min, 4°C/min, 4.2°C/min, 4.5°C/min , 4.8°C/min, 5°C/min, etc.
  • the compaction pressure is 10-30 MPa, for example: 10 MPa, 11 MPa, 12 MPa, 14 MPa, 15 MPa, 18 MPa, 20 MPa, 22 MPa, 24 MPa, 25 MPa, 28 MPa, 29 MPa, 30 MPa, etc.
  • strong graphene oxide refers to graphene oxide with a carbon content of 45-55%
  • weak graphene oxide refers to graphene oxide with a carbon content of 80-90%.
  • This embodiment shows a preparation process of a mixed slurry of strong and weak graphene oxide, which specifically includes the following steps:
  • Step 3) Mix the dispersions obtained in step 1) and step 2), and disperse at a high speed with a linear velocity of 70m/s to obtain a graphene oxide slurry with a solid content of 5.45%.
  • the weak graphene oxide accounts for the weight of the total solids. 16.7%.
  • This embodiment shows a preparation process for preparing a composite film of strong and weak graphene oxide using the process of Example 1A, which specifically includes the following steps:
  • Step 1) Use the process of Example 1A to prepare a mixed slurry of graphene oxide
  • Step 2) The slurry of step 1) is degassed using a continuous on-line degassing machine, the speed of the degassing machine is 2400 r/min, the opening of the feed valve is 30%, and the vacuum negative pressure is 500 Pa.
  • Step 3) The slurry after step 2) is defoamed by a coater.
  • the thickness of the coated wet film is 3 mm, and the continuous coating speed is 1.2 m/min.
  • the drying adopts a 16-section oven with a drying tunnel length of 64m.
  • the temperature of each section of the oven is 60°C, 63°C, 65°C, 70°C, 75 °C, 78°C, 80°C, 85°C, 85°C, 85°C, 85°C, 78°C, 75°C, 70°C, 60°C, obtain strong and weak graphene oxide with a gram weight of 180g/m 2
  • the composite membrane It can be seen from Figure 1 that the use of a small amount of weak graphene oxide does not affect the stacking effect of graphene oxide during assembly, and the graphene oxide stacks well.
  • This embodiment shows a preparation process for preparing a graphene thermally conductive film using the process of Example 1B, which specifically includes the following steps:
  • Step 1) preparing a graphene oxide composite film using the process of Example 1B;
  • Step 3) The graphene foam film obtained in step 2) is compacted to increase its density to obtain a graphene thermally conductive film with a density of 2.1 g/cm 3 , a thermal conductivity of 1560 W/m ⁇ K, and a thickness of 49 ⁇ m.
  • This embodiment shows a preparation process of a mixed slurry of weak and weak graphene oxide, which specifically includes the following steps:
  • Step 1) preparing a strong graphene oxide dispersion: disperse 0.9 kg of strong graphene oxide in 19.1 kg of deionized water to obtain a 4.5% solid content strong graphene oxide dispersion, a total of 20 kg;
  • Step 3) Mix the dispersions obtained in step 1) and step 2), and disperse at a high speed with a linear velocity of 100m/s to obtain a graphene oxide slurry with a solid content of 5%.
  • the weak graphene oxide accounts for the weight of the total solids. 28%.
  • This embodiment shows a preparation process for preparing a composite film of strong and weak graphene oxide using the process of Example 2A, which specifically includes the following steps:
  • Step 1) Use the process of Example 2A to prepare a mixed slurry of graphene oxide
  • Step 2) The slurry of step 1) is degassed using a continuous on-line degassing machine, the speed of the degassing machine is 3000 r/min, the opening of the feed valve is 28%, and the vacuum negative pressure is 500 Pa.
  • Step 3) The slurry after step 2) is defoamed by a coater.
  • the thickness of the coated wet film is 2 mm, and the continuous coating speed is 2 m/min.
  • the drying adopts 16-section oven with a drying tunnel length of 64m.
  • the temperature of each section of the oven is 55°C, 60°C, 63°C, 65°C, 70 °C, 75°C, 78°C, 80°C, 80°C, 80°C, 80°C, 80°C, 80°C, 78°C, 75°C, 70°C, 60°C, obtain strong and weak graphene oxide with a gram weight of 110g/m 2
  • the composite membrane It can be seen from Figure 2 that the use of a small amount of weak graphene oxide does not affect the stacking effect during the assembly of graphene oxide, and the graphene oxide stacks well.
  • This embodiment shows a preparation process for preparing a graphene thermally conductive film using the process of Example 2B, which specifically includes the following steps:
  • Step 1) Prepare graphene oxide composite film using the process of Example 2B;
  • Step 3) The graphene foam film obtained in step 2) is rolled to increase its density to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thermal conductivity of 1232 W/m ⁇ K, and a thickness of 33 ⁇ m.
  • This embodiment shows a preparation process of a mixed slurry of strong and weak graphene oxide, which specifically includes the following steps:
  • Step 1) preparing a strong graphene oxide dispersion: disperse 1.1 kg of strong graphene oxide in 18.9 kg of deionized water to obtain a 5.5% solid content strong graphene oxide dispersion, a total of 20 kg;
  • Step 3) Mix the dispersions obtained in step 1) and step 2) and disperse at high speed with a linear velocity of 300m/s to obtain a graphene oxide slurry with a solid content of 6.44%.
  • the weak graphene oxide accounts for the total solid mass. 46.6%.
  • This embodiment shows a preparation process for preparing a composite film of strong and weak graphene oxide using the process of Example 3A, which specifically includes the following steps:
  • Step 1) Use the process of Example 3A to prepare a mixed slurry of graphene oxide
  • Step 2) The slurry of step 1) is degassed using a continuous online deaerator, the deaerator speed is 2800r/min, the feed valve opening is 30%, and the vacuum negative pressure is 500Pa.
  • Step 3) The slurry after step 2) is defoamed by knife coating with a coater, the thickness of the coated wet film is 3.5 mm, and the continuous coating speed is 1 m/min.
  • the drying adopts a 16-section oven with a drying tunnel length of 64m.
  • the temperature of each section of the oven is 60°C, 63°C, 65°C, 75°C, 80 °C ⁇ 85°C ⁇ 90°C ⁇ 95°C ⁇ 95°C ⁇ 95°C ⁇ 95°C ⁇ 85°C ⁇ 75°C ⁇ 70°C ⁇ 60°C, get strong and weak graphene oxide with gram weight of 248g/m 2 The composite membrane. It can be seen from Figure 3 that the use of a small amount of weak graphene oxide does not affect the stacking effect during the assembly of graphene oxide, and the graphene oxide stacks well.
  • This embodiment shows a preparation process for preparing a graphene thermally conductive film using the process of Example 3B, which specifically includes the following steps:
  • Step 1) The graphene oxide composite film is prepared by the process of Example 3B;
  • Step 2) Heat the composite film, heat up to 100°C at a rate of 1°C/min, then heat up to 300°C at a rate of 0.2°C/min, then heat up to 2600°C at a rate of 4°C/min, and treat for 1 hour , To remove the oxygen-containing functional groups of the composite film to obtain a graphene foam film with a thickness of 150 ⁇ m;
  • Step 3) The graphene foam film obtained in step 2) is compacted to increase its density to obtain a graphene thermally conductive film with a density of 1.95 g/cm 3 , a thermal conductivity of 1120 W/m ⁇ K and a thickness of 85 ⁇ m.
  • This comparative example shows a preparation process of graphene oxide slurry with a strong degree of oxidation, which specifically includes the following steps:
  • This comparative example shows the preparation process of the graphene oxide film prepared by the process of comparative example 4A, which specifically includes the following steps:
  • Step 1) Prepare graphene oxide slurry using the process of Comparative Example 4A;
  • Step 2) The slurry of step 1) is degassed using a continuous on-line degassing machine, the speed of the degassing machine is 2800 r/min, the opening of the feed valve is 30%, and the vacuum negative pressure is 500 Pa.
  • Step 3) Use a coater to coat the slurry after step 2) deaeration, the thickness of the coated wet film is 4.5 mm, and the continuous coating speed is 0.46 m/min.
  • the drying adopts a 16-section oven with a drying tunnel length of 64m.
  • the temperature of each section of the oven is 60°C, 63°C, 65°C, 75°C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 80 °C, 75 °C, 70 °C, 60 °C
  • the graphene oxide film with a gram weight of 135 g/m 2 is obtained. It can be seen from Figure 4 that only strong graphene oxide is used to make graphene oxide stack well.
  • This comparative example shows the preparation process of using the process of comparative example 4B to prepare the graphene thermal conductive film, which specifically includes the following steps:
  • Step 1) The graphene oxide film is prepared by the process of Comparative Example 4B;
  • Step 2) Heat the graphene oxide film, heat up to 100°C at a rate of 1°C/min, then heat up to 300°C at a rate of 0.2°C/min, and then heat up to 2850°C at a rate of 4°C/min, Treat for 1 hour to remove the oxygen-containing functional groups of the graphene oxide film to obtain a graphene foam film with a thickness of 106 ⁇ m;
  • Step 3) The graphene foam film obtained in step 2) is compacted to increase its density to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thermal conductivity of 1605 W/m ⁇ K, and a thickness of 31 ⁇ m.
  • the thickness of the graphene thermally conductive film of 31 ⁇ m obtained in Comparative Example 4 and the graphene thermally conductive film of 33 ⁇ m obtained in Example 2 are basically close, but the coating of Comparative Example 4 needs to be coated with a thicker film, and the coating speed is significantly reduced. The cloth cost is high. To obtain a graphene thermally conductive film with the same thickness, Comparative Example 4 requires a higher cost. By comparing Example 1 and Comparative Example 4, the addition of less weak graphene oxide in Example 1 has less effect on the thermal conductivity.
  • This comparative example shows a preparation process of a weakly oxidized graphene oxide slurry, which specifically includes the following steps:
  • This comparative example shows the preparation process of the graphene oxide film prepared by the process of comparative example 5A, which specifically includes the following steps:
  • Step 1) Prepare graphene oxide slurry using the process of Comparative Example 5A;
  • Step 2) The slurry of step 1) is degassed using a continuous on-line degassing machine, the speed of the degassing machine is 2800 r/min, the opening of the feed valve is 30%, and the vacuum negative pressure is 500 Pa.
  • Step 3) The slurry after step 2) is defoamed by a coater.
  • the thickness of the coated wet film is 2 mm, and the continuous coating speed is 2.3 m/min.
  • the drying adopts a 16-section oven with a drying tunnel length of 64m.
  • the temperature of each section of the oven is 60°C, 63°C, 65°C, 75°C, 80 °C, 85°C, 90°C, 95°C, 95°C, 95°C, 95°C, 95°C, 85°C, 75°C, 70°C, 60°C, the graphene oxide film with a gram weight of 140g/m 2 is obtained.
  • Figure 5 only weak graphene oxide is used to prepare the graphene oxide film. Since the weak graphene oxide contains less oxygen functional groups and the number of peeled layers is small, the stacking effect is not good during assembly.
  • This comparative example shows the preparation process of using the process of comparative example 5B to prepare the graphene thermally conductive film, which specifically includes the following steps:
  • Step 1) The graphene oxide film is prepared by the process of Comparative Example 5B;
  • Step 2) Heat the graphene oxide film, heat up to 100°C at a rate of 1°C/min, then heat up to 300°C at a rate of 0.2°C/min, and then heat up to 2800°C at a rate of 4°C/min, Treat for 1 hour to remove the oxygen-containing functional groups of the graphene oxide film to obtain a graphene foam film with a thickness of 80 ⁇ m;
  • Step 3) The graphene foam film obtained in step 2) is compacted to increase its density to obtain a graphene thermally conductive film with a density of 2.0 g/cm 3 , a thermal conductivity of 736 W/m ⁇ K, and a thickness of 56 ⁇ m.

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Abstract

一种不同氧化程度的氧化石墨烯浆料、氧化石墨烯复合膜和石墨烯导热膜。所述氧化石墨烯浆料包括氧化石墨烯和溶剂，所述氧化石墨烯包括强氧化石墨烯和弱氧化石墨烯。其中浆料中包括两种不同氧化程度的氧化石墨烯，能够提升单位质量的氧化石墨烯中的碳含量，使最终得到的石墨烯导热膜的碳较多。

Description

强、弱氧化石墨烯的混合浆料及其制备方法、强、弱氧化石墨烯的复合膜及其制备方法 技术领域
本发明涉及材料领域，具体涉及用氧化石墨烯制备石墨烯导热膜的工艺。
背景技术
石墨烯具有很好的导热性能，具有广泛的应用前景。通过氧化石墨烯排列组装成氧化石墨烯膜，再进行高温处理制备石墨烯导热膜是常用的一种制备石墨烯导热膜的工艺。通过这种方法制备出的石墨烯导热膜是由多层石墨烯堆叠而成的高定向导热膜，具有机械性能好、导热系数高、质量轻、材料薄、柔韧性好等特点，能够解决电子、航空航天、医疗等行业的散热问题。
现有的技术采用的氧化石墨烯是通过化学氧化石墨得到的氧化石墨烯，具有丰富的含氧官能团，一般碳含量为50％左右。这种氧化石墨烯的排列组装性能好，但是用其制备石墨烯导热膜，单位质量的氧化石墨烯最终得到的导热膜的碳较少，使成本提升，不利于工业生产。背景技术部分的内容仅仅是发明人所知晓的技术，并不当然代表本领域的现有技术。
发明内容
针对现有技术存在问题中的一个或多个，本发明提供一种氧化石墨烯浆料，浆料中包括两种不同氧化程度的氧化石墨烯，能够提升单位质量的氧化石墨烯中的碳含量，使最终得到的石墨烯的导热膜的碳较多。
基于以上目的，本发明提供一种强、弱氧化石墨烯混合浆料，包括氧化石墨烯和溶剂，所述氧化石墨烯包括强氧化石墨烯和弱氧化石墨烯。
本发明的强氧化石墨烯指的是氧化程度强的氧化石墨烯，弱氧化石墨烯指的是氧化程度弱的氧化石墨烯。
氧化石墨烯是通过在石墨的层间加上一些物质和结构，将石墨片层剥离开得到的，达到一定的插层和氧化的程度才可以将其剥离得到很薄的片层(3层及以下)。氧化石墨烯的氧化程度高，含氧官能团多，片层剥离得较薄，在组装成膜时更加有序，组装效果更好，但是强氧化石墨烯的碳含量低，高温处理后得到的石墨烯量较少。弱氧化石墨烯的碳含量高，高温处理后得到的石墨烯的量较多，但是较弱的氧化程度只是在石墨片的边缘进行氧化，无法通过剥离得到片层数较少的氧化石墨烯，通过实验也几乎很难制备氧化程度弱且剥离层数薄的氧化石墨烯。弱氧化石墨烯氧化程度地，含氧官能团少， 剥离时层数较多，如果只采用弱氧化石墨烯进行组装成膜，成膜时得不到高定向的结构，有序性不好，从而影响高温处理后得到的石墨烯导热膜的导热系数的提高。
氧化石墨烯在制备的过程中很难控制氧化程度，目前难以制备氧化程度居于强氧化程度和弱氧化程度之间的氧化石墨烯，且氧化石墨烯的氧化程度稍微下降，片层剥离得不好，就会影响氧化石墨烯成膜时的组装，大幅度影响最终高温处理后制备得到的石墨烯导热膜的导热系数。因此，选择单一的氧化程度的氧化石墨烯不能兼容得到残留的石墨烯的量多且导热性能良好的石墨烯导热膜。
本发明提供一种强、弱氧化石墨烯混合的浆料，在组装成膜的有序性影响不大的情况下，使高温处理后的石墨烯导热膜的量多且石墨烯导热膜的导热性能良好。
根据本发明的一个方面，所述氧化石墨烯的固含量为5-8％。
根据本发明的一个方面，所述弱氧化石墨烯占氧化石墨烯质量的5-50％，优选5-30％，进一步优选10-30％。
根据本发明的一个方面，所述强氧化石墨烯的碳含量为45-55％。
优选地，所述弱氧化石墨烯的碳含量为80-90％。
弱氧化石墨烯的碳含量选择80-90％的范围，是因为碳含量过高的氧化石墨烯剥离时层数较高，组装时有序性会变差。
根据本发明的一个方面，所述溶剂包括水、NMP、DMF中一种或两种以上的混合溶剂。
和不含有含氧官能团的石墨烯不同的是，两种不同氧化程度的氧化石墨烯混合在溶剂中，因两种氧化石墨烯表面都含有亲水性的含氧官能团，并且两者都带有负电荷，在溶剂中相互排斥，不易团聚，具有良好的相互分散的性能。
本发明还提供一种强、弱氧化石墨烯的混合浆料的制备方法，具体包括如下步骤：
分别制备强氧化石墨烯分散液和弱氧化石墨烯分散液，将强氧化石墨烯分散液和弱氧化石墨烯分散液混合，分散，得到强、弱氧化石墨烯的混合浆料。
理论上，强氧化石墨烯和弱氧化石墨烯在溶液中因为表面的官能团带有负电荷-COOH而相互排斥，不易团聚。但是，在实际生产中还是出现团聚问题，得到的浆料的稳定性仍然不够理想。经过多方向的分析之后，本申请发 明人发现团聚的原因并不是氧化石墨烯粒径、比表面和吸油值等问题造成的，而是氧化石墨烯在浆料中呈现的电荷影响了体系。氧化石墨烯分散液因带有-COOH基团呈酸性，分散时需要在分散液中加入碱进行中和。如果直接将两种氧化石墨烯混合再加入碱，因为两种氧化石墨烯的氧化程度不同，其结构上含有的-COOH的量不同，加入碱中和时，会造成反应不均匀，导致分散不好。通过改变工艺程序，先将两种氧化石墨烯分别分散好，氧化石墨烯上的-COOH基团得到充分的中和后，再将两者进行混合，则避免了上述分散不均的问题。因此，先分别将两种氧化石墨烯分散在溶剂中，让氧化石墨烯的-COOH充分中和，再将两者混合，使混合液中的两种氧化石墨烯不容易团聚。
根据本发明的一个方面，强氧化石墨烯分散液的制备方法包括：将经化学氧化法制备而成的氧化石墨烯分散到溶剂中，得到强氧化石墨烯分散液。
优选地，所述化学氧化法为将石墨在强酸溶液中与氧化剂反应，得到氧化石墨烯。
进一步优选地，所述化学氧化法包括Bordie法、Staudenmaier法和Hummers法。
根据本发明的一个方面，强氧化石墨烯分散液中，强氧化石墨烯的固含量为3-8％。
优选地，弱氧化石墨烯分散液中，弱氧化石墨烯的固含量为7-11％。
弱氧化石墨烯因其含有的含氧官能团的量较少，所结合的溶剂少，更容易得到高浓度的浆料；因为弱氧化石墨烯剥离的层数没有强氧化石墨烯的层数少，因此可以得到较高固含量的弱氧化石墨烯分散液。
根据本发明的一个方面，对强氧化石墨烯分散液和弱氧化石墨烯分散液的混合液采用高速分散，分散的线速度是50-300m/s，优选100m/s。
本发明还提供一种强、弱氧化石墨烯的复合膜，包括强氧化石墨烯和弱氧化石墨烯，所述弱氧化石墨烯的含量为5-50％，优选5-30％，进一步优选10-30％。
因为强氧化石墨烯的剥离程度较好，能够帮助弱氧化石墨烯进行有序组装，因弱氧化石墨烯的含碳量高，使得单位质量的氧化石墨烯复合膜制备成的石墨烯导热膜增多，节约了成本。如果只用强氧化石墨烯制备石墨烯导热膜，最终得到的石墨烯导热膜的导热系数高，但是石墨烯导热膜的厚度薄；如果只用弱氧化石墨烯制备石墨烯导热膜，或弱氧化石墨烯的含量过多，因弱氧化的氧化石墨烯很难剥离得到层数少(10层以下)的氧化石墨烯，组装时有序性不好，最终热处理后的石墨烯导热膜的导热系数低；如果只用居中 的氧化程度的氧化石墨烯，其氧化程度比强氧化石墨烯的低，由于氧化程度的降低，使氧化石墨烯的组装受到影响，最终导致热处理后的石墨烯导热膜导热系数偏低。因此，选择弱氧化石墨烯的含量为10-30％，能够得到导热系数较高、碳的残余比例较高的石墨烯导热膜，使成本得到最大程度的降低。
根据本发明的一个方面，所述氧化石墨烯复合膜的克重是100-250g/m 2，优选180g/m 2。
优选地，所述强氧化石墨烯的碳含量为45-55％。
优选地，所述弱氧化石墨烯的碳含量为80-90％。
根据本发明的一个方面，所述复合膜的强氧化石墨烯和弱氧化石墨烯面内定向排列。面内定向排列指的是氧化石墨烯通过氢键组装成膜，在组装成的平面内定向排列，使热处理后的石墨烯导热膜的热量能够沿着石墨烯定向排列的方向传输。
本发明还提供一种强、弱氧化石墨烯的复合膜的制备方法，具体包括如下步骤：
采用所述强、弱氧化石墨烯的混合浆料的制备方法制备强、弱氧化石墨烯的混合浆料；和
将浆料经脱泡、涂布、干燥，形成强、弱氧化石墨烯的复合膜。
根据本发明的一个方面，脱泡采用连续在线脱泡机，转速为2000-3000r/min。
优选地，所述脱泡机的进料阀门开度为25-35％，优选30％。
优选地，所述脱泡机内真空负压为400-600Pa，优选500Pa。
根据本发明的一个方面，涂布的方法包括刮涂和狭缝挤压式涂布，优选刮涂，进一步优选采用涂布机进行刮涂。
狭缝挤压式涂布的方法是让一定流量的浆料从挤压头上料口进入摸头内部型腔，并形成稳定的压力，浆料最后在摸头狭缝出口喷出，涂覆在基材上。
刮涂是采用刮刀进行涂装以制得厚涂膜的一种涂装方式。
优选地，涂布形成湿膜的厚度为2-5mm，优选3mm。因为弱氧化石墨烯的碳含量高，可以提高最终导热膜的碳残余值，这样在相同的氧化石墨烯涂布的厚度情况下，可以得到更厚的石墨烯导热膜。如果需要制备相同厚度的石墨烯导热膜，采用本发明的方法，可以使涂布形成湿膜的厚度更薄，可以大幅度降低制膜成本，提升效率。
优选地，涂布的速度为1-2m/min，优选1.2m/min。
根据本发明的一个方面，干燥的温度为50-100℃，干燥的时间为 0.5-1.5h。
本发明还提供一种石墨烯导热膜，所述石墨烯导热膜的导热系数大于1000W/m·K。
根据本发明的一个方面，所述石墨烯导热膜的密度为1.9-2.1g/cm 3。
优选地，所述石墨烯导热膜的厚度为30-100μm。
本发明还提供一种石墨烯导热膜的制备方法，包括如下步骤：
采用所述强、弱氧化石墨烯的复合膜的制备方法制备强、弱氧化石墨烯的复合膜；
对复合膜进行高温处理；和
压实高温处理后的复合膜，得到石墨烯导热膜。
因为氧化石墨烯复合膜的含碳量较高，高温处理过厚的石墨烯导热膜的量较多，可大幅降低制膜成本，提升效率。
根据本发明的一个方面，所述对复合膜进行高温处理的方法包括：将复合膜从室温升温至1000-3000℃，处理5-15h。
优选地，升温速率为0.2-5℃/min。
进一步优选地，100℃以下时，升温速率为1-1.5℃/min，大于100℃且在300℃以下时，升温速率为0.2-0.5℃/min，大于300℃时，升温速率为3-5℃/min。
根据本发明的一个方面，压实的压力为10-30MPa。
本发明的有益效果是：
本发明采用两种不同程度的氧化石墨烯混合制备石墨烯导热膜，强氧化程度的氧化石墨烯官能团丰富，组装有序性良好，弱氧化程度的氧化石墨烯含碳量高，使制备出的石墨烯导热膜更厚，提高最终残余碳的比例，可以提升生产效率，有效降低成本。浓度相同的强氧化程度的氧化石墨烯浆料和本发明的强、弱氧化石墨烯的混合浆料相比，本发明的浆料只需要涂布2mm的湿膜就能够得到32μm的石墨烯导热膜，而强氧化程度的氧化石墨烯浆料需要涂布4.5mm的湿膜才能得到31μm的石墨烯导热膜；将强氧化程度的氧化石墨烯浆料和强、弱氧化石墨烯的混合浆料分别涂布4.5mm的湿膜，强氧化程度的氧化石墨烯浆料最终得到31μm的石墨烯导热膜，而强、弱氧化石墨烯的混合浆料最终得到72μm的石墨烯导热膜。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。在附图中：
图1是实施例1的氧化石墨烯膜的SEM图；
图2是实施例2的氧化石墨烯膜的SEM图；
图3是实施例3的氧化石墨烯膜的SEM图；
图4是对比例4的氧化石墨烯膜的SEM图；
图5是对比例5的氧化石墨烯膜的SEM图。
具体实施方式
在下文中，仅简单地描述了某些示例性实施例。正如本领域技术人员可认识到的那样，在不脱离本发明的精神或范围的情况下，可通过各种不同方式修改所描述的实施例。因此，附图和描述被认为本质上是示例性的而非限制性的。
以下结合附图对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
作为本发明的第一种实施方式，展示了一种强、弱氧化石墨烯的混合浆料，包括氧化石墨烯和溶剂，所述氧化石墨烯包括强氧化石墨烯和弱氧化石墨烯。氧化石墨烯的固含量为5-8％，例如：5％、5.2％、5.4％、5.5％、5.8％、6％、6.2％、6.5％、6.8％、7％、7.2％、7.5％、7.8％、8％，等。弱氧化石墨烯占氧化石墨烯质量的5-50％，例如：5％、6％、7％、8％、9％、10％、15％、20％、25％、30％、35％、40％、42％、45％、48％、49％、50％，等。强氧化石墨烯的碳含量为45-55％，例如：45％、46％、47％、48％、49％、50％、51％、52％、53％、54％、55％，等。弱氧化石墨烯的碳含量为80-90％，例如：80％、81％、82％、83％、84％、85％、86％、87％、88％、89％、90％，等。作为优选的实施方式，弱氧化石墨烯占氧化石墨烯质量的5-30％，例如：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、19％、20％、22％、25％、28％、29％、30％，等。作为最佳的实施方式，弱氧化石墨烯占氧化石墨烯质量的10-30％，例如：10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、26％、27％、28％、29％、30％，等。弱氧化石墨烯的碳含量选择80-90％的范围，是因为碳含量过高的氧化石墨烯剥离时层数较高，组装时有序性会变差。溶剂包括水、NMP、DMF中一种或两种以上的混合溶剂。
本发明的强氧化石墨烯指的是氧化程度强的氧化石墨烯，弱氧化石墨烯指的是氧化程度弱的氧化石墨烯。
氧化石墨烯是通过在石墨的层间加上一些物质和结构，将石墨片层剥离开得到的，达到一定的插层和氧化的程度才可以将其剥离得到很薄的片层(3层及以下)。氧化石墨烯的氧化程度高，含氧官能团多，片层剥离得较薄，在组装成膜时更加有序，组装效果更好，但是强氧化石墨烯的碳含量低，高温处理后得到的石墨烯量较少。弱氧化石墨烯的碳含量高，高温处理后得到的石墨烯的量较多，但是较弱的氧化程度只是在石墨片的边缘进行氧化，无法通过剥离得到片层数较少的氧化石墨烯，通过实验也几乎很难制备氧化程度弱且剥离层数薄的氧化石墨烯。弱氧化石墨烯氧化程度地，含氧官能团少，剥离时层数较多，如果只采用弱氧化石墨烯进行组装成膜，成膜时得不到高定向的结构，有序性不好，从而影响高温处理后得到的石墨烯导热膜的导热系数的提高。
氧化石墨烯在制备的过程中很难控制氧化程度，目前难以制备氧化程度居于强氧化程度和弱氧化程度之间的氧化石墨烯，且氧化石墨烯的氧化程度稍微下降，就会影响氧化石墨烯成膜时的组装，大幅度影响最终高温处理后制备得到的石墨烯导热膜的导热系数。因此，选择单一的氧化程度的氧化石墨烯不能兼容得到残留的石墨烯的量多且导热性能良好的石墨烯导热膜。
作为本发明的第二种实施方式，展示了一种强、弱氧化石墨烯的混合浆料的制备方法，具体包括如下步骤：
分别制备强氧化石墨烯分散液和弱氧化石墨烯分散液，将强氧化石墨烯分散液和弱氧化石墨烯分散液混合，分散，得到强、弱氧化石墨烯的混合浆料。
理论上，强氧化石墨烯和弱氧化石墨烯在溶液中因为表面的官能团带有负电荷-COOH而相互排斥，不易团聚。但是，在实际生产中还是出现团聚问题，得到的浆料的稳定性仍然不够理想。经过多方向的分析之后，本申请发明人发现团聚的原因并不是氧化石墨烯粒径、比表面和吸油值等问题造成的，而是氧化石墨烯在浆料中呈现的电荷影响了体系。氧化石墨烯分散液因带有-COOH基团呈酸性，分散时需要在分散液中加入碱进行中和。如果直接将两种氧化石墨烯混合再加入碱，因为两种氧化石墨烯的氧化程度不同，其结构上含有的-COOH的量不同，加入碱中和时，会造成反应不均匀，导致分散不好。通过改变工艺程序，先将两种氧化石墨烯分别分散好，氧化石墨烯上的-COOH基团得到充分的中和后，再将两者进行混合，则避免了上述分散不均的问题。因此，先分别将两种氧化石墨烯分散在溶剂中，让氧化石墨烯的-COOH充分中和，再将两者混合，使混合液中的两种氧化石墨烯不容易团聚。
强氧化石墨烯分散液的制备方法包括：将经化学氧化法制备而成的氧化石墨烯分散到溶剂中，得到强氧化石墨烯分散液。化学氧化法为将石墨在强酸溶液中与氧化剂反应，得到氧化石墨烯。化学氧化法包括Bordie法、Staudenmaier法和Hummers法。
强氧化石墨烯分散液中，强氧化石墨烯的固含量为3-8％，例如：3％、4％、5％、6％、7％、8％，等。弱氧化石墨烯分散液中，弱氧化石墨烯的固含量为7-11％，例如：7％、8％、9％、10％、11％，等。弱氧化石墨烯因其含有的含氧官能团的量较少，所结合的溶剂少，更容易得到高浓度的浆料；因为弱氧化石墨烯剥离的层数没有强氧化石墨烯的层数少，因此可以得到较高固含量的弱氧化石墨烯分散液。
对强氧化石墨烯分散液和弱氧化石墨烯分散液的混合液采用高速分散，分散的线速度是50-300m/s，例如：50m/s、60m/s、70m/s、80m/s、90m/s、100m/s、120m/s、150m/s、180m/s、200m/s、220m/s、240m/s、250m/s、280m/s、290m/s、300m/s，等。作为优选的实施方式，分散的线速度是100m/s。
作为本发明的第三种实施方式，展示了一种不强、弱氧化石墨烯的复合膜，包括强氧化石墨烯和弱氧化石墨烯，弱氧化石墨烯的含量为5-50％，例如：5％、6％、7％、8％、9％、10％、15％、20％、25％、30％、35％、40％、42％、45％、48％、49％、50％，等。作为优选的实施方式，弱氧化石墨烯的含量为5-30％，例如：5％、6％、7％、8％、9％、10％、12％、15％、18％、19％、20％、21％、24％、25％、28％、29％、30％，等。作为最佳的实施方式，弱氧化石墨烯的含量为10-30％，例如：10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、26％、27％、28％、29％、30％，等。
因为强氧化石墨烯的剥离程度较好，能够帮助弱氧化石墨烯进行有序组装，因弱氧化石墨烯的含碳量高，使得单位质量的氧化石墨烯复合膜制备成的石墨烯导热膜增多，节约了成本。如果只用强氧化石墨烯制备石墨烯导热膜，最终得到的石墨烯导热膜的导热系数高，但是石墨烯导热膜的厚度薄；如果只用弱氧化石墨烯制备石墨烯导热膜，或弱氧化石墨烯的含量过多，因弱氧化的氧化石墨烯很难剥离得到层数少(10层以下)的氧化石墨烯，组装时有序性不好，最终热处理后的石墨烯导热膜的导热系数低；如果只用居中的氧化程度的氧化石墨烯，其氧化程度比强氧化石墨烯的低，由于氧化程度的降低，使氧化石墨烯的组装受到影响，最终导致热处理后的石墨烯导热膜导热系数偏低。因此，选择弱氧化石墨烯的含量为5-50％，能够得到导热系数较高、碳的残余比例较高的石墨烯导热膜，使成本得到最大程度的降低。
氧化石墨烯复合膜的克重是100-250g/m 2，例如：100g/m 2、110g/m 2、120g/m 2、140g/m 2、150g/m 2、180g/m 2、200g/m 2、220g/m 2、230g/m 2、240g/m 2、250g/m 2，等。作为优选的实施方式，氧化石墨烯复合膜的克重是180g/m 2。强氧化石墨烯的碳含量为45-55％，例如：45％、46％、47％、48％、49％、50％、51％、52％、53％、54％、55％，等。弱氧化石墨烯的碳含量为80-90％，例如：80％、81％、82％、83％、84％、85％、86％、87％、88％、89％、90％，等。氧化石墨烯复合膜的强氧化石墨烯和弱氧化石墨烯面内定向排列。面内定向排列指的是氧化石墨烯通过氢键组装成膜，在组装成的平面内定向排列，使热处理后的石墨烯导热膜的热量能够沿着石墨烯定向排列的方向传输。
作为本发明的第四种实施方式，展示了一种强、弱氧化石墨烯的复合膜的制备方法，具体包括如下步骤：
采用第二种实施方式的方法制备强、弱氧化石墨烯的混合浆料；和
将浆料经脱泡、涂布、干燥，形成强、弱氧化石墨烯的复合膜。
脱泡采用连续在线脱泡机，转速为2000-3000r/min，例如：2000r/min、2100r/min、2200r/min、2300r/min、2400r/min、2500r/min、2600r/min、2700r/min、2800r/min、2900r/min、3000r/min，等。脱泡机的进料阀门开度为25-35％，例如：25％、26％、27％、28％、29％、30％、31％、32％、33％、34％、35％，等。作为优选的实施方式，脱泡机的进料阀门开度为30％。脱泡机内真空负压为400-600Pa，例如：400Pa、420Pa、440Pa、450Pa、480Pa、490Pa、500Pa、520Pa、550Pa、580Pa、590Pa、600Pa，等。作为优选的实施方式，脱泡机内真空负压为500Pa。涂布的方法包括狭缝挤压式涂布和刮涂。狭缝挤压式涂布的方法是让一定流量的浆料从挤压头上料口进入摸头内部型腔，并形成稳定的压力，浆料最后在摸头狭缝出口喷出，涂覆在基材上。刮涂是采用刮刀进行涂装以制得厚涂膜的一种涂装方式。优选采用刮涂的方式，进一步优选采用涂布机进行刮涂。涂布形成湿膜的厚度为2-5mm，例如：2mm、2.2mm、2.5mm、2.8mm、3mm、3.2mm、3.5mm、3.8mm、4mm、4.2mm、4.5mm、4.8mm、5mm，等。作为优选的实施方式，涂布形成湿膜的厚度为3mm。因为弱氧化石墨烯的碳含量高，可以提高最终导热膜的碳残余值，这样在相同的氧化石墨烯涂布的厚度情况下，可以得到更厚的石墨烯导热膜。如果需要制备相同厚度的石墨烯导热膜，采用本发明的方法，可以使涂布形成湿膜的厚度更薄，可以大幅度降低制膜成本，提升效率。涂布的速度为1-2m/min，例如：1m/min、1.1m/min、1.2m/min、1.3m/min、1.4m/min、1.5m/min、1.6m/min、1.7m/min、1.8m/min、1.9m/min、2m/min，等。作为优选的实施方式，涂布 的速度为1.2m/min。干燥的温度为50-100℃，例如：50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃，等；干燥的时间为0.5-1.5h，例如：0.5h、0.6h、0.7h、0.8h、0.9h、1.0h、1.1h、1.2h、1.3h、1.4h、1.5h，等。
作为本发明的第五种实施方式，展示了一种石墨烯导热膜，所述石墨烯导热膜的导热系数大于1000W/m·K，例如：1100W/m·K、1200W/m·K、1300W/m·K、1400W/m·K、1500W/m·K、1600W/m·K、1700W/m·K、1800W/m·K，等。石墨烯导热膜的密度为1.9-2.1g/cm 3，例如：1.9g/cm 3、1.92g/cm 3、19.5g/cm 3、19.8g/cm 3、2.0g/cm 3、2.02g/cm 3、2.05g/cm 3、2.08g/cm 3、2.1g/cm 3，等。石墨烯导热膜的厚度为30-100μm，例如：30μm、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm、75μm、80μm、85μm、90μm、95μm、100μm，等。
作为本发明的第六种实施方式，展示了一种石墨烯导热膜的制备方法，包括如下步骤：
采用第四种实施方式的方法制备强、弱氧化石墨烯的复合膜；
对复合膜进行高温处理；和
压实高温处理后的复合膜，得到石墨烯导热膜。
因为氧化石墨烯复合膜的含碳量较高，高温处理过厚的石墨烯导热膜的量较多，可大幅降低制膜成本，提升效率。
对复合膜进行高温处理的方法包括：将复合膜从室温升温至1000-3000℃，例如：1000℃、1200℃、1500℃、1800℃、2000℃、2200℃、2500℃、2800℃、3000℃，等；处理5-15h，例如：5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h，等。升温速率为0.2-5℃/min，例如：0.2℃/min、0.3℃/min、0.4℃/min、0.5℃/min、0.8℃/min、1℃/min、1.5℃/min、2℃/min、2.5℃/min、3℃/min、3.5℃/min、4℃/min、4.5℃/min、4.8℃/min、4.9℃/min、5℃/min，等。作为优选的实施方式，100℃以下时，升温速率为1-1.5℃/min，例如：1℃/min、1.1℃/min、1.2℃/min、1.3℃/min、1.4℃/min、1.5℃/min，等；大于100℃且在300℃以下时，升温速率为0.2-0.5℃/min，例如：0.2℃/min、0.3℃/min、0.4℃/min、0.5℃/min，等；大于300℃时，升温速率为3-5℃/min，例如：3℃/min、3.2℃/min、3.5℃/min、3.8℃/min、4℃/min、4.2℃/min、4.5℃/min、4.8℃/min、5℃/min，等。压实的压力为10-30MPa，例如：10MPa、11MPa、12MPa、14MPa、15MPa、18MPa、20MPa、 22MPa、24MPa、25MPa、28MPa、29MPa、30MPa，等。
下面通过实施例和对比例对本发明的优越性进行阐述。以下实施例中，强氧化石墨烯是指碳含量为45-55％的氧化石墨烯；弱氧化石墨烯是指碳含量为80-90％的氧化石墨烯。
实施例1A：
本实施例示出了一种强、弱氧化石墨烯的混合浆料的制备工艺，具体包括如下步骤：
步骤1)：制备强氧化石墨烯分散液：将1kg强氧化石墨烯分散在19kg的去离子水中，得到5％固含量的强氧化石墨烯分散液，共20kg；
步骤2)：制备弱氧化石墨烯分散液：将0.2kg弱氧化石墨烯分散在1.8kg的去离子水中，得到10％固含量的弱氧化石墨烯分散液，共2kg；
步骤3)：将步骤1)和步骤2)得到的分散液进行混合，高速分散，线速度为70m/s，得到5.45％固含量的氧化石墨烯浆料，弱氧化石墨烯占总固体质量的16.7％。
实施例1B：
本实施例示出了采用实施例1A的工艺制备强、弱氧化石墨烯的复合膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例1A的工艺制备氧化石墨烯的混合浆料；
步骤2)：对步骤1)的浆料采用连续在线脱泡机进行脱泡，脱泡机转速为2400r/min，进料阀门开度30％，真空负压500Pa。
步骤3)：对步骤2)脱泡后的浆料采用涂布机刮涂，涂布湿膜的厚度为3mm，连续涂布的速度是1.2m/min。
步骤4)：对步骤3)涂布完成后的湿膜进行干燥，干燥采用烘道长度为64m的16节烘箱，每节烘箱的温度分别是60℃、63℃、65℃、70℃、75℃、78℃、80℃、85℃、85℃、85℃、85℃、85℃、78℃、75℃、70℃、60℃，得到克重是180g/m 2的强、弱氧化石墨烯的复合膜。由图1可以看出，采用少量的弱氧化石墨烯，不会影响氧化石墨烯组装时堆叠效果，氧化石墨烯堆叠良好。
实施例1C：
本实施例示出了采用实施例1B的工艺制备石墨烯导热膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例1B的工艺制备氧化石墨烯的复合膜；
步骤2)：对复合膜进行热处理，以1.5℃/min的速率升温至100℃，再以0.2℃/min的速率升温至300℃，再以5℃/min的速率升温至3000℃，处理1h，除去复合膜的含氧官能团，得到厚度为90μm的石墨烯泡沫膜；
步骤3)：对步骤2)得到的石墨烯泡沫膜通过压实提高其密度，得到密度为2.1g/cm 3，导热系数是1560W/m·K，厚度为49μm的石墨烯导热膜。
实施例2A：
本实施例示出了一种不强、弱氧化石墨烯的混合浆料的制备工艺，具体包括如下步骤：
步骤1)：制备强氧化石墨烯分散液：将0.9kg强氧化石墨烯分散在19.1kg的去离子水中，得到4.5％固含量的强氧化石墨烯分散液，共20kg；
步骤2)：制备弱氧化石墨烯分散液：将0.35kg弱氧化石墨烯分散在4.65kg的去离子水中，得到7％固含量的弱氧化石墨烯分散液，共5kg；
步骤3)：将步骤1)和步骤2)得到的分散液进行混合，高速分散，线速度为100m/s，得到5％固含量的氧化石墨烯浆料，弱氧化石墨烯占总固体质量的28％。
实施例2B：
本实施例示出了采用实施例2A的工艺制备强、弱氧化石墨烯的复合膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例2A的工艺制备氧化石墨烯的混合浆料；
步骤2)：对步骤1)的浆料采用连续在线脱泡机进行脱泡，脱泡机转速为3000r/min，进料阀门开度28％，真空负压500Pa。
步骤3)：对步骤2)脱泡后的浆料采用涂布机刮涂，涂布湿膜的厚度为2mm，连续涂布的速度是2m/min。
步骤4)：对步骤3)涂布完成后的湿膜进行干燥，干燥采用烘道长度为64m的16节烘箱，每节烘箱的温度分别是55℃、60℃、63℃、65℃、70℃、75℃、78℃、80℃、80℃、80℃、80℃、80℃、78℃、75℃、70℃、60℃，得到克重是110g/m 2的强、弱氧化石墨烯的复合膜。由图2可以看出，采用少量的弱氧化石墨烯，不会影响氧化石墨烯组装时堆叠效果，氧化石墨烯堆叠良好。
实施例2C：
本实施例示出了采用实施例2B的工艺制备石墨烯导热膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例2B的工艺制备氧化石墨烯复合膜；
步骤2)：对复合膜进行热处理，以1℃/min的速率升温至100℃，再以0.5℃/min的速率升温至300℃，再以3℃/min的速率升温至2800℃，处理1h，除去复合膜的含氧官能团，得到厚度为60μm的石墨烯泡沫膜；
步骤3)：对步骤2)得到的石墨烯泡沫膜通过辊压提高其密度，得到密度为2.0g/cm 3，导热系数是1232W/m·K，厚度为33μm的石墨烯导热膜。
实施例3A：
本实施例示出了一种强、弱氧化石墨烯的混合浆料的制备工艺，具体包括如下步骤：
步骤1)：制备强氧化石墨烯分散液：将1.1kg强氧化石墨烯分散在18.9kg的去离子水中，得到5.5％固含量的强氧化石墨烯分散液，共20kg；
步骤2)：制备弱氧化石墨烯分散液：将0.96kg弱氧化石墨烯分散在11.04kg的去离子水中，得到8％固含量的弱氧化石墨烯分散液，共12kg；
步骤3)：将步骤1)和步骤2)得到的分散液进行混合，高速分散，线速度为300m/s，得到6.44％固含量的氧化石墨烯浆料，弱氧化石墨烯占总固体质量的46.6％。
实施例3B：
本实施例示出了采用实施例3A的工艺制备强、弱氧化石墨烯的复合膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例3A的工艺制备氧化石墨烯的混合浆料；
步骤2)：对步骤1)的浆料采用连续在线脱泡机进行脱泡，脱泡机转速为2800r/min，进料阀门开度30％，真空负压500Pa。
步骤3)：对步骤2)脱泡后的浆料采用涂布机刮涂，涂布湿膜的厚度为3.5mm，连续涂布的速度是1m/min。
步骤4)：对步骤3)涂布完成后的湿膜进行干燥，干燥采用烘道长度为64m的16节烘箱，每节烘箱的温度分别是60℃、63℃、65℃、75℃、80℃、85℃、90℃、95℃、95℃、95℃、95℃、95℃、85℃、75℃、70℃、60℃，得到克重是248g/m 2的强、弱氧化石墨烯的复合膜。由图3可以看出，采用少量的弱氧化石墨烯，不会影响氧化石墨烯组装时堆叠效果，氧化石墨烯堆叠良好。
实施例3C：
本实施例示出了采用实施例3B的工艺制备石墨烯导热膜的制备工艺，具体包括如下步骤：
步骤1)：采用实施例3B的工艺制备氧化石墨烯复合膜；
步骤2)：对复合膜进行热处理，以1℃/min的速率升温至100℃，再以0.2℃/min的速率升温至300℃，再以4℃/min的速率升温至2600℃，处理1h，除去复合膜的含氧官能团，得到厚度为150μm的石墨烯泡沫膜；
步骤3)：对步骤2)得到的石墨烯泡沫膜通过压实提高其密度，得到密度为1.95g/cm 3，导热系数是1120W/m·K，厚度为85μm的石墨烯导热膜。
对比例4A：
本对比例示出了一种强氧化程度的氧化石墨烯浆料的制备工艺，具体包括如下步骤：
将0.6kg强氧化石墨烯分散在19.4kg的去离子水中，得到3％固含量的强氧化石墨烯浆料，共20kg。
对比例4B：
本对比例示出了采用对比例4A的工艺制备氧化石墨烯膜的制备工艺，具体包括如下步骤：
步骤1)：采用对比例4A的工艺制备氧化石墨烯浆料；
步骤2)：对步骤1)的浆料采用连续在线脱泡机进行脱泡，脱泡机转速为2800r/min，进料阀门开度30％，真空负压500Pa。
步骤3)：对步骤2)脱泡后的浆料采用涂布机刮涂，涂布湿膜的厚度为4.5mm，连续涂布的速度是0.46m/min。
步骤4)：对步骤3)涂布完成后的湿膜进行干燥，干燥采用烘道长度为64m的16节烘箱，每节烘箱的温度分别是60℃、63℃、65℃、75℃、80℃、80℃、80℃、80℃、80℃、80℃、80℃、80℃、80℃、75℃、70℃、60℃，得到克重是135g/m 2的氧化石墨烯膜。由图4可以看出，只采用强氧化石墨烯，令氧化石墨烯堆叠良好。
对比例4C：
本对比例示出了采用对比例4B的工艺制备石墨烯导热膜的制备工艺，具体包括如下步骤：
步骤1)：采用对比例4B的工艺制备氧化石墨烯膜；
步骤2)：对氧化石墨烯膜进行热处理，以1℃/min的速率升温至100℃，再以0.2℃/min的速率升温至300℃，再以4℃/min的速率升温至2850℃，处理1h，除去氧化石墨烯膜的含氧官能团，得到厚度为106μm的石墨烯泡沫膜；
步骤3)：对步骤2)得到的石墨烯泡沫膜通过压实提高其密度，得到密度为2.0g/cm 3，导热系数是1605W/m·K，厚度为31μm的石墨烯导热膜。
对比例4得到31μm的石墨烯导热膜和实施例2得到的33μm的石墨烯导热膜，厚度基本接近，但是涂布时对比例4需要涂布更厚的膜，涂布的速度明显降低，涂布成本高。得到相同厚度的石墨烯导热膜，对比例4需要付出更高的成本。通过对比实施例1和对比例4，实施例1加入少的弱氧化石墨烯对导热系数的影响较小。
对比例5A：
本对比例示出了一种弱氧化程度的氧化石墨烯浆料的制备工艺，具体包括如下步骤：
将1.4kg弱氧化石墨烯分散在18.6kg的去离子水中，得到7％固含量的弱氧化石墨烯浆料，共20kg。
对比例5B：
本对比例示出了采用对比例5A的工艺制备氧化石墨烯膜的制备工艺，具体包括如下步骤：
步骤1)：采用对比例5A的工艺制备氧化石墨烯浆料；
步骤2)：对步骤1)的浆料采用连续在线脱泡机进行脱泡，脱泡机转速为2800r/min，进料阀门开度30％，真空负压500Pa。
步骤3)：对步骤2)脱泡后的浆料采用涂布机刮涂，涂布湿膜的厚度为2mm，连续涂布的速度是2.3m/min。
步骤4)：对步骤3)涂布完成后的湿膜进行干燥，干燥采用烘道长度为64m的16节烘箱，每节烘箱的温度分别是60℃、63℃、65℃、75℃、80℃、85℃、90℃、95℃、95℃、95℃、95℃、95℃、85℃、75℃、70℃、60℃，得到克重是140g/m 2的氧化石墨烯膜。由图5可以看出，只采用弱氧化石墨烯制备氧化石墨烯膜，由于弱氧化石墨烯含氧官能团少，剥离的层数少，组装时堆叠效果不好。
对比例5C：
本对比例示出了采用对比例5B的工艺制备石墨烯导热膜的制备工艺，具体包括如下步骤：
步骤1)：采用对比例5B的工艺制备氧化石墨烯膜；
步骤2)：对氧化石墨烯膜进行热处理，以1℃/min的速率升温至100℃，再以0.2℃/min的速率升温至300℃，再以4℃/min的速率升温至2800℃，处理1h，除去氧化石墨烯膜的含氧官能团，得到厚度为80μm的石墨烯泡沫膜；
步骤3)：对步骤2)得到的石墨烯泡沫膜通过压实提高其密度，得到密度为2.0g/cm 3，导热系数是736W/m·K，厚度为56μm的石墨烯导热膜。
由于对比例5B的氧化石墨烯膜的组装效果不好，导致最终高温处理后的石墨烯导热膜导热系数低。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种强、弱氧化石墨烯的混合浆料，其特征在于，包括氧化石墨烯和溶剂，所述氧化石墨烯包括强氧化石墨烯和弱氧化石墨烯。
  2. 根据权利要求1所述的强、弱氧化石墨烯的混合浆料，其特征在于，所述氧化石墨烯的固含量为5-8％；
    优选地，所述弱氧化石墨烯占氧化石墨烯质量的5-50％，优选5-30％，进一步优选10-30％；
    优选地，所述强氧化石墨烯的碳含量为45-55％；
    优选地，所述弱氧化石墨烯的碳含量为80-90％；
    优选地，所述溶剂包括水、NMP、DMF中一种或两种以上的混合溶剂。
  3. 一种强、弱氧化石墨烯的混合浆料的制备方法，其特征在于，包括如下步骤：
    分别制备强氧化石墨烯分散液和弱氧化石墨烯分散液，将强氧化石墨烯分散液和弱氧化石墨烯分散液混合，分散，得到强、弱氧化石墨烯的混合浆料。
  4. 根据权利要求3所述的强、弱氧化石墨烯的混合浆料的制备方法，其特征在于，强氧化石墨烯分散液的制备方法包括将经化学氧化法制备而成的氧化石墨烯分散到溶剂中，得到强氧化石墨烯分散液；进一步优选地，所述化学氧化法为将石墨在强酸溶液中与氧化剂反应，得到氧化石墨烯；进一步优选地，化学氧化法包括Brodie法、Staudenmaier法和Hummers法；
    优选地，强氧化石墨烯分散液中，强氧化石墨烯的固含量为3-8％；
    优选地，弱氧化石墨烯分散液中，弱氧化石墨烯的固含量为7-11％；
    优选地，对强氧化石墨烯分散液和弱氧化石墨烯分散液的混合液采用高速分散，分散的线速度是50-300m/s，优选100m/s。
  5. 一种强、弱氧化石墨烯的复合膜，其特征在于，包括强氧化石墨烯和弱氧化石墨烯，所述弱氧化石墨烯的含量为5-50％，优选5-30％，进一步优选10-30％；
    优选地，所述强氧化石墨烯的碳含量为45-55％；
    优选地，所述弱氧化石墨烯的碳含量为80-90％；
    优选地，所述氧化石墨烯复合膜的克重是100-250g/m 2，优选180g/m 2；
    优选地，所述氧化石墨烯复合膜的强氧化石墨烯和弱氧化石墨烯面内定向排列。
  6. 一种强、弱氧化石墨烯的复合膜的制备方法，其特征在于，包括如下步骤：
    采用权利要求3或4的方法制备强、弱氧化石墨烯的混合浆料；和
    将浆料经脱泡、涂布、干燥，形成强、弱氧化石墨烯的复合膜。
  7. 根据权利要求6所述的强、弱氧化石墨烯的复合膜的制备方法，其特征在于，脱泡采用连续在线脱泡机，转速为2000-3000r/min；进一步优选地，所述脱泡机的进料阀门开度为25-35％，优选30％；进一步优选地，所述脱泡机内真空负压为400-600Pa，优选500Pa；
    优选地，涂布的方法包括刮涂和狭缝挤压式涂布，优选刮涂，进一步优 选采用涂布机进行刮涂；
    优选地，涂布形成湿膜的厚度为2-5mm，优选3mm；
    优选地，涂布的速度为1-2m/min，优选1.2m/min；
    优选地，干燥的温度为50-100℃，干燥的时间为0.5-1.5h。
  8. 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大于1000W/m·K；
    优选地，所述石墨烯导热膜的密度为1.9-2.1g/cm 3；
    优选地，所述石墨烯导热膜的厚度为30-100μm。
  9. 一种石墨烯导热膜的制备方法，其特征在于，包括如下步骤：
    采用权利要求6或7的方法制备强、弱氧化石墨烯的复合膜；
    对复合膜进行高温处理；和
    压实高温处理后的复合膜，得到石墨烯导热膜。
  10. 根据权利要求9所述的石墨烯导热膜的制备方法，其特征在于，所述对复合膜进行高温处理的方法包括：将复合膜从室温升温至1000-3000℃，处理5-15h；
    优选地，升温速率为0.2-5℃/min；进一步优选地，100℃以下时，升温速率为1-1.5℃/min，大于100℃且在300℃以下时，升温速率为0.2-0.5℃/min，大于300℃时，升温速率为3-5℃/min；
    优选地，所述压实的压力为10-30MPa。
PCT/CN2020/111173 2019-09-06 2020-08-26 强、弱氧化石墨烯的混合浆料及其制备方法、强、弱氧化石墨烯的复合膜及其制备方法 WO2021043030A1 (zh)

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