CN114958193A - Graphene-based temperature control coating and preparation method thereof - Google Patents

Graphene-based temperature control coating and preparation method thereof Download PDF

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CN114958193A
CN114958193A CN202210583268.7A CN202210583268A CN114958193A CN 114958193 A CN114958193 A CN 114958193A CN 202210583268 A CN202210583268 A CN 202210583268A CN 114958193 A CN114958193 A CN 114958193A
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graphene
coating
radiation
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composite coating
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CN114958193B (en
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何朋
丁古巧
曾宪喆
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract

The invention relates to a graphene-based temperature control coating which covers a base material and comprises a heat conduction-radiation seamless series connection heat dissipation gradient structure formed by high heat conduction graphene powder and high radiation graphene powder, wherein the mass ratio of the high heat conduction graphene powder to the high radiation graphene powder is changed from 1: 0.01-1: 0.1 to 1: 1-1: 5 in a gradient manner from one side close to the base material to the other side far away from the base material. The invention also relates to a preparation method of the graphene-based temperature control coating, wherein the high-thermal-conductivity graphene-based composite coating and the high-radiation graphene-based composite coating are respectively coated on the substrate in a dynamic mode or are coated after being dynamically mixed, the loading rate of the high-thermal-conductivity graphene-based composite coating is gradually reduced during coating, and the loading rate of the high-radiation graphene-based composite coating is gradually increased. The graphene-based temperature control coating can fully exert the synergistic effect of two heat transfer channels of high heat conduction and high radiation, and realizes effective regulation and control of the temperature of the base material.

Description

Graphene-based temperature control coating and preparation method thereof
Technical Field
The invention relates to a thermal control coating structure and a coating thereof, in particular to a graphene-based temperature control coating and a preparation method thereof.
Background
With the continuous development of integrated circuit processing technology, the integration level of devices is continuously improved, and the internal power density of the devices is also continuously increased, so that waste heat of electronic devices cannot be timely discharged to form local hot spots, and the working stability and the service life of the devices are seriously influenced. The failure probability of the electronic device increases sharply with the increase of the working temperature, and according to statistics, the working life of the device is reduced by 50 percent when the environmental temperature is increased by 10 ℃. Therefore, timely removal of the large amount of waste heat generated by device operation is critical to ensure device reliability and long lifetime. At present, the thermal management technology of electronic devices becomes a bottleneck problem that Moore's law is difficult to continue to improve and the integration level and performance are difficult to continue to improve. The development of efficient heat dissipation technology is urgently needed, heat accumulated inside the electronic device is discharged and dissipated to the external environment, and the internal working temperature of the device is guaranteed to be within a safe and controllable range. In addition, the new energy automobile industry is rapidly developed in recent years, and a huge new energy automobile market becomes a necessary place for each large automobile enterprise. The power battery is used as a core component of the new energy automobile, and the safety and the reliability are the preconditions of large-scale application. However, the power battery cell generates a certain amount of heat during the charging and discharging process, and if the heat is not dissipated to the environment in time, the internal temperature of the cell can be continuously increased, so that the aging of the cell material is accelerated. When the temperature exceeds a certain range, the diaphragm inside the battery core can lose effectiveness, so that the thermal runaway of the battery is caused, and finally accidents such as battery core combustion and explosion are caused. Therefore, the safety problem of the power battery is a key problem to be solved urgently in the industry chain of the new energy vehicle, and the key problem is to break through the thermal control technology of the battery.
The temperature control coating technology is an important scheme for controlling the temperature of a device and a system, and the graphene material has advantages in the aspect of improving the temperature control capability of the coating. Researches show that the single atomic layer graphene is the material with the highest heat conductivity coefficient in known materials, and theoretical calculation values and experimental test data of the heat conductivity coefficient are obviously higher than those of known metals, inorganic non-metals and other carbon materials, so that the graphene is very suitable for being used as a heat-conducting filler to prepare a high-performance interface heat-conducting composite material. When the graphene-based composite material is coated on the substrate in the form of the coating, the heat of the substrate can be timely conducted out of the coating, and then the heat is transferred to the environment through the coating, so that the temperature of the substrate is finally reduced. CN202111034320.5 discloses a graphene heat dissipation coating, which enables graphene to have the ability of forming a heat conduction path in the coating, that is, the ability of forming a heat conduction path in the coating by graphene is improved by adding heat conduction particles with different particle sizes to bridge graphene and filler particles, so as to reduce interface scattering and increase heat dissipation performance of the coating. In addition, graphene has higher heat radiation efficiency compared to a metal material. Therefore, CN202111301285.9, CN202110871129.x, CN202110643316.2, CN202110845517.0, and the like disclose various preparation methods of graphene-based heat dissipation coatings, which mainly improve the infrared radiation coefficient of the composite coating by adding a graphene material, and transfer heat away in a radiation heat dissipation manner, thereby reducing the surface temperature of an object.
In fact, for temperature-controlled coating technology, the thermal conductivity and radiation performance of the coating must be considered at the same time, and the coating should be able to quickly absorb the heat of the object and radiate the absorbed heat to the environment with high efficiency. However, the existing research and technology has many problems in preparing temperature control coating by using graphene: on the one hand, neglecting the control of physical properties of graphene materials, it is roughly thought that graphene materials have excellent thermal conductivity and radiation performance at the same time. In fact, graphene materials obtained by different preparation methods have great difference in structure and physical properties, and many physical properties are even mutually exclusive. High thermal conductivity requires that graphene be thin and have good lattice quality, while high radiance requires that defects and crystal lattice distortion exist in the graphene lattice structure to reduce crystal structure symmetry and promote molecular polarization and infrared radiation. Therefore, a composite system of a graphene material and even a plurality of graphene materials of similar structures cannot simultaneously give consideration to excellent heat conductivity and high radiation efficiency. On the other hand, the reasonable design of the coating structure is lacked in the aspect of coordinating two ways of heat conduction and radiation of the coating, and the synergistic effect of the heat conduction and the radiation in the aspect of improving the temperature control performance of the coating cannot be fully exerted by the uniform coating structure prepared by the prior art.
Disclosure of Invention
In order to solve the problem that the coating in the prior art cannot simultaneously give consideration to excellent heat conductivity, high radiation efficiency and the like, the invention provides a graphene-based temperature control coating and a preparation method thereof.
According to one aspect of the present invention, a graphene-based temperature control coating is provided, which covers a substrate and includes a heat conduction-radiation seamless series connection heat dissipation gradient structure composed of high heat conduction graphene powder and high radiation graphene powder, wherein the contents of the high heat conduction graphene powder and the high radiation graphene powder are respectively distributed in a gradient manner in a thickness direction of the graphene-based temperature control coating; the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder is changed from 1: 0.01-1: 0.1 to 1: 1-1: 5 in a gradient manner from one side close to the base material to the other side far away from the base material.
Preferably, the defect density of the high-thermal-conductivity graphene powder is less than 9 × 10 10 cm -2 . That is, the high thermal conductivity graphene powder is high lattice quality graphene. In a preferred embodiment, the high thermal conductivity graphene powder is prepared by a liquid phase exfoliation method. In a preferred embodiment, the defect density of the high thermal conductivity graphene powder is 2.4 × 10 10 cm -2 。
Preferably, the defect density of the high-radiation graphene powder is more than 4 × 10 12 cm -2 . It should be understood that the high-emissivity graphene powder is high-defect graphene, including graphene with a large number of defects in the structure such as porous graphene, graphene quantum dots, heteroatom-doped graphene, and the like. In a preferred embodiment, the high-emissivity graphene powder is reduced graphene oxide powder. In a preferred embodiment, the high-radiation graphene powder is nitrogen-doped graphene or boron-doped graphene powder. In a preferred embodiment, the defect density of the high-emissivity graphene powder is 5.3 × 10 13 ～8.4×10 13 cm -2 (e.g., 6.7X 10) 13 ～7.2×10 13 cm -2 )。
Preferably, the longitudinal thermal conductivity of the heat conduction-radiation seamless series heat dissipation gradient structure is greater than 6.5W/(m.K), and the thermal emissivity is greater than 0.94.
Preferably, the thermally conductive-radiating seamless series thermal gradient structure further comprises a structural adhesive. It should be understood that the thermally conductive-radiative seamless series thermal gradient structure further comprises an additive.
According to another aspect of the present invention, there is provided a preparation method of the graphene-based temperature control coating, including the following steps: s1, providing the high-thermal-conductivity graphene-based composite coating through the high-thermal-conductivity graphene powder, and providing the high-radiation graphene-based composite coating through the high-radiation graphene powder; s2, dynamically coating the high-thermal-conductivity graphene-based composite coating and the high-radiation graphene-based composite coating on the substrate simultaneously, wherein the loading rate of the high-thermal-conductivity graphene-based composite coating is gradually reduced and the loading rate of the high-radiation graphene-based composite coating is gradually increased during coating, so that the initial coating loading rate ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder is 1: 0.01-1: 0.1 (the loading rate of the graphene powder is the product of the loading rate of the coating and the concentration of graphene in the corresponding composite coating), the final coating loading rate ratio is 1: 1-1: 5, or S2', coating a dynamic mixture of the high-thermal-conductivity graphene-based composite coating and the high-radiation graphene-based composite coating on the substrate, the content of the high-thermal-conductivity graphene-based composite coating in the dynamic mixture is gradually reduced, and the content of the high-radiation graphene-based composite coating is gradually increased, the initial mixing and loading rate ratio of the high-thermal conductivity graphene powder to the high-radiation graphene powder is 1: 0.01-1: 0.1, and the final mixing and loading rate ratio is 1: 1-1: 5.
Preferably, the high-thermal-conductivity graphene-based composite coating comprises 1-10% of high-thermal-conductivity graphene powder, 40-60% of a structural adhesive, 30-60% of a dispersion medium and 0.5-5% of an auxiliary agent. In a preferred embodiment, the high thermal conductivity graphene-based composite coating comprises 2-6% (e.g., 5%) of high thermal conductivity graphene powder, 50-60% of a structural adhesive, 30-45% (e.g., 32%) of a dispersion medium, and 3-4% of an auxiliary agent.
Preferably, the high-radiation graphene-based composite coating comprises 1-20% of high-radiation graphene powder, 40-60% of a structural adhesive, 20-50% of a dispersion medium and 0.5-5% of an auxiliary agent. In a preferred embodiment, the high-radiation graphene-based composite coating comprises 2-18% (e.g., 10-12%) of high-radiation graphene powder, 45-55% (e.g., 50%) of a structural adhesive, 25-45% (e.g., 32-40%) of a dispersion medium, and 2-3% of an auxiliary agent.
Preferably, the structural adhesive is one or more of silicone resin, silicate, ethyl silicate, silica sol, phosphate. In a preferred embodiment, the structural adhesive is an epoxy modified silicone resin, an S-830 silica sol, or an ethyl orthosilicate based liquid. In a preferred embodiment, the tetraethoxysilane base liquid refers to an ethanol solution of tetraethoxysilane to which water and hydrochloric acid are added.
Preferably, the dispersion medium is one or more of water, toluene, xylene, N-methylpyrrolidone, N-dimethylformamide, ethyl acetate and acetone. It is to be understood that the dispersion medium is a solvent that dissolves and/or disperses the other components.
Preferably, the auxiliary agent is one or more of a dispersing agent, a wetting agent, a defoaming agent, an anti-settling agent, an anti-flash rust agent, a tackifier, a thickening rheological auxiliary agent, a leveling agent, a film forming auxiliary agent and a curing agent.
Preferably, the step S1 includes: the graphene powder and the structural adhesive are respectively dispersed in a dispersion medium and then mixed, or the graphene powder is dispersed in a uniform mixing system of the structural adhesive and the dispersion medium, or the graphene powder is dispersed in the structural adhesive and then added into the dispersion medium, and finally, the auxiliary agent is added and uniformly mixed.
Preferably, the initial coating flow ratio of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating in the step S2 is 1: 0.01-1: 0.05 (e.g., 1: 0.017-1: 0.025), and the coating flow ratio before the coating is finished is 1: 1-1: 3 (e.g., 1: 1.5-1: 2).
Preferably, the initial mixing flow ratio of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating in the step S2' is 1: 0.01-1: 0.05 (e.g., 1: 0.017-1: 0.025), and the mixing flow ratio before the coating is finished is 1: 1-1: 3 (e.g., 1: 1.5-1: 2).
Preferably, the coating in step S2 or S2' is spray coating or spin coating.
Preferably, the substrate in step S2 or S2' is an inorganic non-metal, metal or organic material.
According to the graphene-based temperature control coating, high-thermal-conductivity graphene powder and high-radiation graphene powder are used as fillers, the gradient distribution of the two graphene materials in the coating thickness direction is regulated and controlled simultaneously in a dynamic coating or dynamic mixture coating mode, a high-thermal-conductivity, high-radiation, thermal-conductivity and radiation seamless series connection heat dissipation gradient structure from a heat source to the environment is constructed, the longitudinal thermal conductivity coefficient is larger than 6.5W/(m.K), the thermal radiation coefficient is larger than 0.94, the synergistic effect of two heat transfer channels of high thermal conductivity and high radiation can be fully exerted, the coating is promoted to efficiently absorb the redundant heat on the surface of the substrate and radiate and transfer the redundant heat to the surrounding environment, the effective regulation and control of the temperature of the substrate are realized, namely the heat in the substrate is efficiently transferred to the low-temperature environment, the surface temperature of the substrate is rapidly reduced, and the coating can bear the highest temperature of more than 500 ℃, the method is suitable for thermal management application of high-temperature and high-heat-flux systems, and can be used for improving comprehensive energy efficiency and working stability of high-heat-flux equipment such as high-power electronic devices, new energy automobile systems, household high-energy consumption appliances, high-temperature boilers and the like.
Drawings
FIG. 1 is a graph of spray flow rate of the coating material of example 1 over time.
Fig. 2A is a raman spectrum plot of the graphene material with high thermal conductivity in example 1.
Fig. 2B is a raman spectroscopy profile of the high-emissivity graphene material in example 1.
FIG. 3 is a graph of the thermal weight loss of the temperature controlled coating prepared in example 1.
FIG. 4 is a graph of the spray flow rate of the coating material of example 2 over time.
Fig. 5A is a raman spectrum graph of the high thermal conductivity graphene material in example 2.
Fig. 5B is a raman spectroscopy profile of the high-emissivity graphene material in example 2.
FIG. 6 is a thermogravimetric plot of the temperature controlled coating prepared in example 2.
Fig. 7 is a time-dependent flow rate graph of each flow rate pump in example 3.
Fig. 8A is a raman spectrum graph of the high thermal conductivity graphene material in example 3.
Fig. 8B is a raman spectroscopy profile of the high-emissivity graphene material in example 3.
FIG. 9 is a thermogravimetric plot of the temperature controlled coating prepared in example 3.
Fig. 10 is a time-dependent flow rate graph of each flow rate pump in example 4.
Fig. 11A is a raman spectrum graph of the high thermal conductivity graphene material in example 4.
Fig. 11B is a raman spectroscopy profile map of the high-emissivity graphene material in example 4.
FIG. 12 is a graph of the thermal weight loss of the temperature controlled coating prepared in example 4;
FIG. 13 is a schematic flow diagram of a manufacturing process according to the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Aiming at the problems of material selection and structural design of the existing graphene temperature control coating technology, the inventor finds that the requirements on different thicknesses of the coating are different for improving the temperature control capability of the coating through systematic experimental research: near the interface of the coating and the object, the heat-conducting property of the coating is improved, so that the heat of the object can be quickly conducted into the coating; and near the interface of the coating and the environment, the radiation performance of the coating is improved, so that the heat of the coating is favorably promoted to be dissipated to the environment. The prior art has few considerations, and the realization of the heat conduction and radiation cooperative structure has great technical difficulty from the preparation point of view. Therefore, the whole process of heat dissipation of the object through the coating must be considered from two aspects of heat conduction and radiation, the graphene-based temperature control coating is designed and optimized on the graphene material and structure level, and the temperature control performance of the graphene-based temperature control coating is improved, so that the graphene-based temperature control coating is pushed to be widely applied to the fields of high-power-density electronic devices, high-temperature boilers, power battery systems and the like. Referring to fig. 13, the graphene-based temperature control coating provided by the invention can fully utilize and cooperatively enhance the high thermal conductivity and high radiation performance of graphene materials with different structures through a gradient coating structure constructed by high thermal conductivity graphene powder and high emissivity graphene powder, so that the comprehensive heat dissipation capacity of the graphene coating is remarkably improved, and the cooling capacity of the graphene gradient composite coating is superior to that of a temperature control coating using a single graphene material and a conventional structure as a heat transfer functional unit. The present invention has been completed based on this finding.
In the description of the present invention, percent (%) means weight percent unless otherwise specified.
In the description of the present invention, "plural" means two or more.
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention will be further described in detail through the embodiments. It is obvious that the embodiments described below are only examples of the invention, and that for a person skilled in the art, other embodiments can be derived from the embodiments without inventive step.
Example 1
The performance parameters of the graphene materials used in this example are shown in table 1 below.
TABLE 1
Material High lattice quality graphene Reduced graphene oxide
Type (B) High heat conduction filler High radiationFiller material
Defect concentration (cm) -2 ) 2.4×10 10 5.3×10 13
Transverse thermal conductivity (W/(m.K)) 1537.1 122.6
Longitudinal thermal conductivity (W/(m.K)) 5.3 1.1
Thermal emissivity 0.81 0.95
1.1 composition of graphene-based composite coating (calculated by weight percent):
1.1.1 composition of high-thermal-conductivity graphene-based composite coating
2% of high-thermal-conductivity graphene powder material: 2% of high-lattice-quality graphene powder (prepared by a liquid phase shear stripping method, the average thickness of a lamella is less than 3nm, and physical parameters are shown in the table 1 above);
50% of structural adhesive: epoxy modified silicone resin (epoxy value 0.04-0.07, solid content 50%);
45% of a dispersion medium: n-methylpyrrolidone (ACS, 98%);
3% of other auxiliary agents: 1% of flatting agent (bike BYK-310) and 2% of anti-settling agent (bike RHEOBYK-410).
1.1.2 composition of high-radiation graphene-based composite coating
2% of high-radiation graphene powder material: the reduced graphene oxide powder (prepared by the method of Hummer's oxidized graphene and heat-treated at 500 ℃ for 10s, the average thickness of a lamella is less than 2nm, and the physical parameters are shown in the table 1) is 2%, the Raman spectrum (shown in the figure 2A and the figure 2B) shows the structural difference between the high-thermal-conductivity graphene and the high-radiation graphene, the structural defect peak of the high-thermal-conductivity graphene is weak, and the structural defect peak of the high-radiation graphene is very strong;
50% of structural adhesive: epoxy modified silicone resin (epoxy value 0.04-0.07, solid content 50%);
45% of a dispersion medium: n-methylpyrrolidone (ACS, 98%);
3% of other auxiliary agents: 1% of flatting agent (bike BYK-310) and 2% of anti-settling agent (bike RHEOBYK-410).
1.2 preparation method of the composite coating:
1.2.1 preparation of high-thermal-conductivity graphene-based composite coating
Weighing the following raw materials in parts by weight: 2g of high-lattice-quality graphene powder, 50g of epoxy modified organic silicon resin and 45g N-methyl pyrrolidone for later use;
adding 2g of high-lattice-quality graphene powder into 45g N-methyl pyrrolidone for shearing and dispersing, wherein the shearing rate is 10000rpm, and the shearing time is 2h to obtain a dispersion liquid A;
and adding 50g of epoxy organic silicon resin into the obtained dispersion liquid A, stirring for 1h at 800rpm, continuously stirring, and adding a leveling agent and an anti-settling agent to obtain the high-thermal-conductivity graphene-based composite coating.
1.2.2 preparation of high-radiation graphene-based composite coating
Weighing the following raw materials in parts by weight: 2g of reduced graphene oxide powder, 50g of epoxy modified organic silicon resin and 45g N-methyl pyrrolidone for later use;
adding 2g of reduced graphene oxide powder into 45g N-methyl pyrrolidone, and shearing and dispersing at a shearing rate of 10000rpm for 2h to obtain a dispersion liquid B;
and adding 50g of epoxy organic silicon resin into the obtained dispersion liquid B, stirring for 1h at 800rpm, continuously stirring, and adding a leveling agent and an anti-settling agent to obtain the high-radiation graphene-based composite coating.
1.3 preparation method of temperature-controlled coating
The spray equipment used in this example was an OERTER APL 6.2 automatic spray coater.
Adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
setting the initial spraying flow ratio of the spraying spray gun A and the spraying spray gun B to be 1:0.05 (the spraying flow rate of the spraying spray gun A is 120ml/min, the spraying flow rate of the spraying spray gun B is 6ml/ml, and the initial coating loading rate ratio of the corresponding high-thermal-conductivity graphene powder and high-radiation graphene powder is 1:0.05, namely the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder on the side, close to the substrate, of the composite coating is 1: 0.05);
and simultaneously spraying the coating on the stainless steel substrate by the spraying spray gun A and the spraying spray gun B, wherein in the spraying process, the spraying flow of the spraying spray gun A is set to gradually decrease along with time, the spraying flow of the spraying spray gun B is set to gradually increase along with time, and the total spraying flow of the spraying spray gun A and the spraying spray gun B is kept unchanged. Before spraying, the spraying flow ratio of the spraying gun A to the spraying gun B is 1:3 (the spraying flow rate of the spraying gun A is 31ml/min, the spraying flow rate of the spraying gun B is 95ml/min, and the final state coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:3, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating far away from the substrate is 1:3), the total spraying time is 40s, and the spraying flow rate change condition of each spraying gun in the spraying process is shown in figure 1;
and (3) heating the obtained stainless steel base material coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Example 2
The performance parameters of the graphene materials used in this example are shown in table 2 below.
TABLE 2
Material High lattice quality graphene Nitrogen-doped graphene
Types of High heat conduction filler High radiation filler
Defect concentration (cm) -2 ) 2.4×10 10 6.7×10 13
Transverse thermal conductivity (W/(m.K)) 1537.1 105.3
Longitudinal thermal conductivity (W/(m.K)) 5.3 0.7
Thermal emissivity 0.81 0.96
2.1 composition of graphene-based composite coating (calculated by weight percent):
2.1.1 composition of high-thermal-conductivity graphene-based composite coating
High heat conduction graphene powder material 6%: high-lattice-quality graphene powder (prepared by a liquid phase stripping method, the average thickness of a lamella is less than 3nm, and physical parameters are shown in the table 2) is 6%;
60% of structural adhesive: s-830 silica sol;
30% of a dispersion medium: deionized water;
4% of other auxiliary agents: 2% of dispersant (Keying KYC-9366) and 2% of anti-settling agent (bike RHEOBYK-420).
2.1.2 composition of high-radiation graphene-based composite coating
18% of graphene powder material: the nitrogen-doped graphene (with 6.25 at.% of nitrogen, the average thickness of a sheet layer being less than 2nm, and the physical parameters shown in table 2 above) is 18%, and a raman spectrum (fig. 5A and 5B) shows the structural difference between the high thermal conductivity graphene and the high radiation graphene, wherein the structural defect peak of the high thermal conductivity graphene is weak, and the structural defect peak of the high radiation graphene is very strong;
structural adhesive 53%: s-830 silica sol;
25% of a dispersion medium: deionized water;
4% of other auxiliary agents: 2% of dispersant (Keying KYC-9366) and 2% of anti-settling agent (bike RHEOBYK-420).
2.2 preparation method of the composite coating:
2.2.1 preparation of high-thermal-conductivity graphene-based composite coating
Weighing the following raw materials in parts by weight: 6g of high-lattice-quality graphene powder, 60g S-830 g of silica sol and 30g of deionized water for later use;
uniformly mixing 60g S-830 silica sol with 30g of deionized water, and stirring for 15min at 800rpm to obtain diluted silica sol A;
6g of high-lattice-quality graphene powder, a dispersing agent and an anti-settling agent are added into the obtained diluted silica sol A, and shearing dispersion is carried out at a shearing rate of 10000rpm for 2 hours to obtain the high-thermal-conductivity graphene-based composite coating.
2.2.2 preparation of high-radiation graphene-based composite coating
Weighing the following raw materials in parts by weight: 18g of nitrogen-doped graphene, 53g S-830 silica sol and 25g of deionized water for later use;
uniformly mixing 53g S-830 silica sol with 25g of deionized water, and stirring for 15min at 800rpm to obtain diluted silica sol A;
adding 18g of nitrogen-doped graphene, a dispersing agent and an anti-settling agent into the obtained diluted silica sol A, and carrying out shear dispersion at a shear rate of 10000rpm for 2 hours to obtain the high-radiation graphene-based composite coating.
2.3 preparation method of temperature-controlled coating
The spray equipment used in this example was an OERTER APL 6.2 automatic spray coater.
Adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
setting the initial spraying flow ratio of the spraying spray gun A and the spraying spray gun B to be 1:0.01 (the spraying flow rate of the spraying spray gun A is 180ml/min, the spraying flow rate of the spraying spray gun B is 2ml/ml, and the initial coating loading rate ratio of the corresponding high-thermal-conductivity graphene powder and high-radiation graphene powder is 1:0.03, namely the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder on the side, close to the substrate, of the composite coating is 1: 0.03);
and the spraying spray gun A and the spraying spray gun B spray the coating on the glass plate base material simultaneously, in the spraying process, the spraying flow of the spraying spray gun A is reduced along with time, the spraying flow of the spraying spray gun B is increased along with time, and the total spraying flow of the spraying spray gun A and the spraying spray gun B is kept unchanged. Before spraying, the spraying flow ratio of the spraying gun A to the spraying gun B is 1:1 (the spraying flow rate of the spraying gun A is 91ml/min, the spraying flow rate of the spraying gun B is 91ml/ml, and the final state coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:3, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating far away from the substrate is 1:3), the total spraying time is 40s, and the spraying flow rate change condition of each spraying gun in the spraying process is shown in FIG. 4;
and (3) heating the obtained glass plate substrate coated with the coating in an oven at 60 ℃ for 48h to cure the coating, and taking out the glass plate coated with the coating after the heating is finished.
Example 3
The performance parameters of the graphene materials used in this example are shown in table 3 below.
TABLE 3
Material High lattice quality graphene Boron-doped graphene
Type (B) High heat conduction filler High radiation filler
Defect concentration (cm) -2 ) 2.4×10 10 7.2×10 13
Transverse thermal conductivity (W/(m.K)) 1537.1 94.8
Longitudinal thermal conductivity (W/(m.K)) 5.3 0.3
Thermal emissivity 0.81 0.97
3.1 composition of graphene-based composite coating (calculated by weight percent):
3.1.1 composition of high thermal conductivity graphene-based composite coating
5% of graphene powder material: 5% of high-lattice-quality graphene powder (prepared by a liquid phase stripping method, the average thickness of a lamella is less than 3nm, and physical parameters are shown in the table 3 above);
60% of structural adhesive: ethyl orthosilicate base solution (the preparation process is shown in 3.2.1);
32% of a dispersion medium: deionized water;
3% of other auxiliary agents: 2% of dispersant (Keying KYC-9366) and 1% of anti-settling agent (bike RHEOBYK-420).
3.1.2 composition of high-radiation graphene-based composite coating
10% of graphene powder material: 10% of boron-doped graphene powder (the boron content is 11.5 at.%, the average thickness of a sheet layer is less than 2nm, and the physical property parameter is shown by x 2); raman spectra (fig. 8A and 8B) show the structural difference between the high thermal conductivity graphene and the high radiation graphene, the structural defect peak of the high thermal conductivity graphene is weak, and the structural defect peak of the high radiation graphene is very strong;
55% of structural adhesive: ethyl orthosilicate base solution (the preparation process is shown in 3.2.1);
32% of a dispersion medium: deionized water;
3% of other auxiliary agents: 2% of dispersant (Keying KYC-9366) and 1% of anti-settling agent (bike RHEOBYK-420).
3.2 preparation method of graphene-based composite coating:
3.2.1 preparation of Ethyl orthosilicate based solution
Weighing Ag tetraethoxysilane and B g ethanol, adding the Ag tetraethoxysilane and the B g ethanol into a reaction kettle, uniformly mixing at the stirring speed of 800rpm, and slowly adding C g deionized water and D g 37% hydrochloric acid in the stirring process to obtain a mixed solution 1, wherein the mass ratio of the components A to B to C to D is 60:30:15: 1;
heating the obtained mixed solution 1 to 80 ℃, and reacting for 4 hours at constant temperature to obtain tetraethoxysilane base solution.
3.2.2 preparation of high thermal conductivity graphene-based composite coating
Weighing the following raw materials in parts by weight: 5g of high-lattice-quality graphene powder, 60g of tetraethoxysilane base liquid (the preparation process is shown in 3.2.1) and 32g of deionized water for later use;
adding 32g of deionized water into 60g of tetraethoxysilane base liquid, and stirring for 1 hour at 800rpm to obtain diluted tetraethoxysilane base liquid A;
and adding 5g of high-lattice-quality graphene powder, a dispersing agent and an anti-settling agent into the obtained tetraethoxysilane base liquid A, and shearing and dispersing the mixture, wherein the shearing rate is 10000rpm, and the shearing time is 2 hours, so as to obtain the high-thermal-conductivity graphene-based composite coating.
3.2.3 preparation of high-radiation graphene-based composite coating
Weighing the following raw materials in parts by weight: 10g of boron-doped graphene powder, 55g of tetraethoxysilane base solution (the preparation flow is shown in 3.2.1) and 32g of deionized water for later use;
adding 32g of deionized water into 55g of tetraethoxysilane base liquid, and stirring for 1h at 800rpm to obtain diluted tetraethoxysilane base liquid A;
and adding 10g of boron-doped graphene powder, a dispersing agent and an anti-settling agent into the obtained tetraethoxysilane base liquid A, and shearing and dispersing at a shearing rate of 10000rpm for 2 hours to obtain the high-radiation graphene-based composite coating.
3.3 preparation method of temperature-controlled coating
The spray equipment used in this example was an OERTER APL 6.2 automatic spray coater.
Adding the high-thermal-conductivity graphene-based composite coating into the container A;
adding the high-radiation graphene-based composite coating into the container B;
respectively pumping the high-thermal-conductivity graphene-based composite coating in the container A and the high-radiation graphene-based composite coating in the container B into the container C by using a flow pump A and a flow pump B for mixing;
the mixed paint in the container C is pumped into a spray gun by a flow pump C for spraying operation, and the mixed paint is sprayed on the aluminum substrate. During the spraying process, the flow of the flow pump A is gradually reduced along with the time, the flow of the flow pump B is gradually increased along with the time, and the total flow of the flow pump A and the flow pump B and the flow of the flow pump C are kept unchanged. The flow ratio of the flow pump A to the flow pump B at the beginning of spraying is 1:0.025 (the flow of the flow pump A is 200ml/min, the flow of the flow pump B is 5ml/min, the flow of the flow pump C is 205ml/min, the initial mixing loading rate ratio of the corresponding high thermal conductivity graphene powder and the high radiation graphene powder is 1:0.05, namely the mass ratio of the high thermal conductivity graphene powder and the high radiation graphene powder on the side of the composite coating close to the substrate is 1:0.05), the flow ratio before spraying is 1:1.5 (the flow of the flow pump A is 82ml/min, the flow of the flow pump B is 123ml/min, the flow of the flow pump C is 205ml/min, and the final coating loading rate ratio of the corresponding high thermal conductivity graphene powder and the high radiation graphene powder is 1:3, namely the mass ratio of the high thermal conductivity graphene powder and the high radiation graphene powder on the side of the composite coating away from the substrate is 1:3), the total spraying time is 40s, and the flow change condition of each flow pump in the spraying process is shown in figure 7;
and (3) heating the obtained aluminum plate coated with the coating in an oven at 150 ℃ for 4h, curing the coating, and taking out the aluminum plate coated with the coating after the heating is finished.
Example 4
The performance parameters of the graphene materials used in this example are shown in table 4 below.
TABLE 4
Material High lattice quality graphene Sulfur-doped graphene
Type (B) High heat conduction filler High radiation filler
Defect concentration (cm) -2 ) 2.4×10 10 8.4×10 13
Transverse thermal conductivity (W/(m.K)) 1537.1 75.2
Longitudinal thermal conductivity (W/(m.K)) 5.3 0.1
Rate of thermal radiation 0.81 0.98
4.1 composition of graphene-based composite coating (calculated by weight percent):
4.1.1 composition of high-thermal-conductivity graphene-based composite coating
2% of graphene powder material: 2% of high-lattice-quality graphene powder (prepared by a liquid phase stripping method, the average thickness of a lamella is less than 3nm, and physical parameters are shown in the table 4 above);
50% of structural adhesive: epoxy modified silicone resin (epoxy value 0.04-0.07, solid content 50%);
45% of a dispersion medium: xylene (ACS, 98.5%);
3% of other auxiliary agents: 1% of leveling agent (BYK-310) and 2% of anti-settling agent (BYK RHEOBYK-410).
4.1.2 high-radiation graphene-based composite coating compositionBecome into
12% of graphene powder material: 2% of sulfur-doped graphene powder (the sulfur content is 12.8 at.%, the average thickness of a sheet layer is less than 3nm, and the physical property parameters are shown in the table 4 above); raman spectra (fig. 11A and 11B) show the structural difference between the high thermal conductivity graphene and the high radiation graphene, the structural defect peak of the high thermal conductivity graphene is weak, and the structural defect peak of the high radiation graphene is very strong;
45% of structural adhesive: epoxy modified silicone resin (epoxy value 0.04-0.07, solid content 50%);
40% of a dispersion medium: xylene (ACS, 98.5%);
3% of other auxiliary agents: 1% of flatting agent (bike BYK-310) and 2% of anti-settling agent (bike RHEOBYK-410).
4.2 preparation method of graphene-based composite coating:
4.2.1 preparation of high-thermal-conductivity graphene-based composite coating
Weighing the following raw materials in parts by weight: 2g of high-lattice-quality graphene powder, 50g of epoxy modified organic silicon resin and 45g of xylene for later use;
adding 2g of high-lattice-quality graphene powder into 45g of dimethylbenzene, and shearing and dispersing at a shearing rate of 10000rpm for 2h to obtain a dispersion liquid A;
and adding 50g of epoxy organic silicon resin into the obtained dispersion liquid A, stirring for 1h at 800rpm, continuously stirring, and adding a leveling agent and an anti-settling agent to obtain the high-thermal-conductivity graphene-based composite coating.
4.2.2 preparation of high-radiation graphene-based composite coating
Weighing the following raw materials in parts by weight: 12g of sulfur-doped graphene powder, 45g of epoxy modified organic silicon resin and 40g of xylene for later use;
adding 40g of dimethylbenzene into 45g of epoxy modified organic silicon resin, and uniformly stirring to obtain diluted epoxy organic silicon resin A;
and adding 12g of sulfur-doped graphene powder, a leveling agent and an anti-settling agent into the obtained epoxy organic silicon resin A, and shearing and dispersing at a shearing rate of 10000rpm for 2 hours to obtain the high-radiation graphene-based composite coating.
4.3 preparation method of temperature-controlled coating
The spin coating apparatus used in this embodiment is a Raeb AC200-PE program-controlled servo spin coater.
Adding the high-thermal-conductivity graphene-based composite coating into the container A;
adding the high-radiation graphene-based composite coating into the container B;
respectively pumping the high-thermal-conductivity graphene-based composite coating in the container A and the high-radiation graphene-based composite coating in the container B into the container C by using a flow pump A and a flow pump B for mixing;
and pumping the mixed coating in the container C into a dropper of a spin coater by using a flow pump C for spin coating, and spin-coating the mixed coating on the tinplate substrate. During the spin coating process, the flow rate of the flow pump A is gradually reduced along with the time, the flow rate of the flow pump B is gradually increased along with the time, and the total flow rate of the flow pump A and the flow pump B and the flow rate of the flow pump C are kept unchanged. The flow ratio of the flow pump A to the flow pump B at the beginning of spin coating is 1:0.017 (the flow of the flow pump A is 120ml/min, the flow of the flow pump B is 2ml/ml, the flow of the flow pump C is 122ml/ml, the initial mixing loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:0.1, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating close to the substrate is 1:0.1), the flow ratio before the end of spin coating is 1:0.45 (the flow of the flow pump A is 84ml/min, the flow of the flow pump B is 38ml/ml, the flow of the flow pump C is 122ml/ml, and the final mixing loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:2.7, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating away from the substrate is 1:2.7), the total time of the spin-coating operation is 40s, and a graph 10 is shown between flow change conditions of all flow pumps in the spin-coating process;
and (3) heating the obtained tinplate coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the tinplate coated with the coating after the heating is finished.
Comparative example 1
In comparison with example 1, this comparative example uses only the highly thermally conductive graphene-based composite coating in the process of preparing the temperature-controlled coating. The composition and preparation of the high thermal conductivity graphene-based composite coating refer to the descriptions in 1.1.1 and 1.2.1. The preparation method of the temperature control coating comprises the following steps:
spraying the high-thermal-conductivity graphene-based composite coating on a stainless steel plate;
and (3) heating the stainless steel plate coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 2
In comparison with example 1, this comparative example uses only the high-emissivity graphene-based composite coating in the process of preparing the temperature-controlled coating. The composition and preparation of the high-radiation graphene-based composite coating are described in reference to 1.1.2 and 1.2.2. The preparation method of the temperature control coating comprises the following steps:
spraying the high-radiation graphene-based composite coating on a stainless steel plate;
and (3) heating the stainless steel plate coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 3
Compared with example 1, in the process of preparing the temperature control coating, in this comparative example, the initial spraying flow ratio of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating is adjusted to 1:0.2 (the initial coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the corresponding high radiation graphene powder is 1:0.2, that is, the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating close to the substrate is 1: 0.2). The composition and preparation of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are referred to the descriptions in 1.1 and 1.2. The preparation method of the temperature control coating comprises the following steps:
adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
setting the initial spraying flow ratio of the spraying spray gun A and the spraying spray gun B to be 1:0.2 (the spraying flow rate of the spraying spray gun A is 120ml/min, the spraying flow rate of the spraying spray gun B is 24ml/ml, and the initial coating loading rate ratio of the corresponding high-thermal-conductivity graphene powder to the high-radiation graphene powder is 1:0.2, namely the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder on the side, close to the substrate, of the composite coating is 1: 0.2);
and the spraying spray gun A and the spraying spray gun B spray the coating on the stainless steel substrate simultaneously, and in the spraying process, the spraying flow of the spraying spray gun A is reduced along with time, the spraying flow of the spraying spray gun B is increased along with time, and the total spraying flow of the spraying spray gun A and the spraying spray gun B is kept unchanged. Before spraying, the spraying flow ratio of a spraying gun A to a spraying gun B is 1:3 (the spraying flow rate of the spraying gun A is 36ml/min, the spraying flow rate of the spraying gun B is 108ml/ml, and the final state coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:3, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating far away from the substrate is 1:3), and the total spraying time is 35 s;
and (3) heating the obtained stainless steel base material coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 4
Compared with example 1, in the comparative example, in the process of preparing the temperature control coating, the spraying flow ratio of the high thermal conductivity graphene-based composite coating to the high emissivity graphene-based composite coating before the spraying is finished is adjusted to be 1: 0.5. The composition and preparation of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are referred to the records in 1.1 and 1.2. The preparation method of the temperature control coating comprises the following steps:
adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
setting the initial spraying flow ratio of the spraying spray gun A and the spraying spray gun B to be 1:0.05 (the spraying flow rate of the spraying spray gun A is 120ml/min, the spraying flow rate of the spraying spray gun B is 6ml/ml, and the initial coating loading rate ratio of the corresponding high-thermal-conductivity graphene powder and high-radiation graphene powder is 1:0.05, namely the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder on the side, close to the substrate, of the composite coating is 1: 0.05);
and the spraying spray gun A and the spraying spray gun B spray the coating on the stainless steel substrate simultaneously, and in the spraying process, the spraying flow of the spraying spray gun A is reduced along with time, the spraying flow of the spraying spray gun B is increased along with time, and the total spraying flow of the spraying spray gun A and the spraying spray gun B is kept unchanged. Before spraying, the spraying flow ratio of a spraying gun A to a spraying gun B is 1:0.5 (the spraying flow rate of the spraying gun A is 84ml/min, the spraying flow rate of the spraying gun B is 42ml/ml, the final state coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:0.5, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating far away from the substrate is 1:0.5), and the total spraying time is 40 s;
and (3) heating the obtained stainless steel base material coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 5
Compared with example 1, in the comparative example, in the process of preparing the temperature control coating, the spraying flow ratio of the high thermal conductivity graphene-based composite coating to the high radiation graphene-based composite coating before the spraying is finished is adjusted to be 1: 8. The composition and preparation of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are referred to the descriptions in 1.1 and 1.2. The preparation method of the temperature control coating comprises the following steps:
adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
setting the initial spraying flow ratio of the spraying spray gun A and the spraying spray gun B to be 1:0.05 (the spraying flow rate of the spraying spray gun A is 120ml/min, the spraying flow rate of the spraying spray gun B is 6ml/ml, and the initial coating loading rate ratio of the corresponding high-thermal-conductivity graphene powder and high-radiation graphene powder is 1:0.05, namely the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder on the side, close to the substrate, of the composite coating is 1: 0.05);
and the spraying spray gun A and the spraying spray gun B spray the coating on the stainless steel substrate simultaneously, and in the spraying process, the spraying flow of the spraying spray gun A is reduced along with time, the spraying flow of the spraying spray gun B is increased along with time, and the total spraying flow of the spraying spray gun A and the spraying spray gun B is kept unchanged. Before spraying, the spraying flow ratio of a spraying gun A to a spraying gun B is 1:8 (the spraying flow rate of the spraying gun A is 14ml/min, the spraying flow rate of the spraying gun B is 112ml/ml, and the final state coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:8, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder on the side of the composite coating far away from the substrate is 1:8), and the total spraying time is 40 s;
and (3) heating the obtained stainless steel base material coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 6
Compared with example 1, in the process of preparing the temperature control coating, the spraying flow ratio of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating in the spraying process is not changed, and the concentration of each graphene material in the obtained temperature control coating is uniformly distributed but not changed in a gradient manner. The composition and preparation of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are referred to the descriptions in 1.1 and 1.2. The preparation method of the temperature control coating comprises the following steps:
adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
the spraying flow ratio of the spraying spray gun A to the spraying spray gun B is set to be 1:1 (the spraying flow rate of the spraying spray gun A is 63ml/min, the spraying flow rate of the spraying spray gun B is 63ml/ml, and the coating loading rate ratio of the corresponding high thermal conductivity graphene powder to the high radiation graphene powder is 1:1, namely the mass ratio of the high thermal conductivity graphene powder to the high radiation graphene powder at different positions of the composite coating is 1: 1);
spraying the coating on the stainless steel substrate by using the spraying spray gun A and the spraying spray gun B simultaneously, wherein the total spraying time is 40 s;
and (3) heating the obtained stainless steel base material coated with the coating in an oven at 180 ℃ for 3h, curing the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Comparative example 7
Compared with example 1, in the process of preparing the temperature control coating, the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are not sprayed at the same time in the comparative example, but a layer of the high thermal conductivity graphene-based composite coating is sprayed on the substrate, and then a layer of the high radiation graphene-based composite coating is sprayed, so that the temperature control coating forms a double-coating structure rather than a single-layer gradient coating structure. The composition and preparation of the high thermal conductivity graphene-based composite coating and the high radiation graphene-based composite coating are referred to the descriptions in 1.1 and 1.2. The preparation method of the temperature control coating comprises the following steps:
adding the high-thermal-conductivity graphene-based composite coating into a spraying spray gun A;
spraying the high-thermal-conductivity graphene-based composite coating on the stainless steel substrate by using a spraying gun A, wherein the spraying flow rate is 63ml/min, and the spraying time is 40 s;
placing the obtained stainless steel base material coated with the coating in an oven at 100 ℃ for heating for 1h, and performing coating pre-curing;
adding the high-radiation graphene-based composite coating into a spraying spray gun B;
spraying the high-radiation graphene-based composite coating on the stainless steel substrate by using a spraying gun B at the spraying flow rate of 63ml/min for 40 s;
placing the obtained stainless steel base material coated with the coating in an oven at 100 ℃ for heating for 1h, and performing coating pre-curing;
and (3) heating the oven to 180 ℃ for 3h to finally solidify the coating, and taking out the stainless steel plate coated with the coating after the heating is finished.
Test method
The resistance temperature test method is a thermal weight loss curve, namely a change curve of the weight of the coating curing powder along with the temperature increase (10 ℃/min) is tested under the air atmosphere, and the heating temperature when the weight of the coating curing powder is reduced to below 85% of the initial weight is the highest resistance temperature of the coating.
The heat dispersion test method comprises placing the coated metal substrate and the uncoated metal substrate on a constant power heat source (30W, 400cm area) 2 ) And respectively measuring the average temperature of the metal base material in the equilibrium state, and evaluating the cooling amplitude of the coating, namely the heat dissipation capacity, through the difference of the average temperatures of the metal base material and the metal base material.
The infrared radiance test method is that the normal reflectivity of the surface of the object to be tested is measured by adopting the active blackbody radiation source, and then the normal emissivity of the object in a specific infrared band is measured.
The heat conductivity coefficient test of the graphene material adopts a laser scattering method, the graphene material is pressed into a film material with the same thickness (30 mu m) and similar density (2.0 g/cm3), and then the transverse and longitudinal heat conductivity coefficients are tested. The method for testing the thermal conductivity of the coating comprises the steps of putting the coating and the coated substrate into a thermal conductivity tester for testing, and deducting the influence of the substrate from the test result through calculation to obtain the thermal conductivity of the coating in the thickness direction.
The results of the performance test of the coatings obtained in examples 1 to 4 and comparative examples 1 to 7 are shown in Table 5 below.
TABLE 5
Figure BDA0003664983680000191
As can be seen from table 5 above, the graphene-based temperature control coating of the present invention has excellent properties, which are shown in the following: the tolerance temperature is high, and the service temperature is above 550 ℃ (obtained by analyzing the thermal weight loss curve of fig. 3, fig. 6, fig. 9 and fig. 12); the longitudinal thermal conductivity is high, the longitudinal thermal conductivity of the coating in all the embodiments is higher than 6.5W/(m.K) and can reach 7.56W/(m.K), and the heat generated by a heat source can be effectively transferred to the surface of the coating; the emissivity is high, the emissivity of the coating in all embodiments is above 0.94, and the heat on the surface of the coating can be quickly diffused to the surrounding environment in a radiation heat dissipation mode; the heat dissipation effect is obvious, and when the temperature of a heat source is about 500 ℃, the temperature reduction amplitude of the coating is larger than 90 ℃. And the preparation process of the coating and the coating is simple and easy for large-scale production, and the large-scale application of the graphene-based temperature control coating technology in high-heat-flux devices and systems is promoted. In comparative example 1, the temperature control coating only contains high thermal conductivity graphene, and although the coating has high thermal conductivity, the heat generated by the heat source can be quickly conducted to the temperature control coating, the emissivity of the coating is low, and the heat cannot be diffused to the surrounding environment in time, so that the cooling effect is not ideal. In comparative example 2, the temperature control coating only contains high-emissivity graphene, and although the coating has a high emissivity, the heat is not smoothly conducted from the heat source to the surface of the coating, which also results in an undesirable cooling effect. In comparative example 3 and comparative example 5, the spraying flow ratio of the high-emissivity graphene-based composite coating is relatively high, which causes the heat conductivity coefficient of the coating to be reduced, and affects the heat dissipation performance of the coating. In comparative example 4, the spraying flow ratio of the high-emissivity graphene-based composite coating is low, which causes the radiation coefficient of the coating to be reduced, and also affects the heat dissipation performance of the coating. In comparative example 6, the concentrations of the high-emissivity graphene filler and the high-thermal-conductivity graphene filler in the coating have no gradient change, and the advantages of the high-emissivity graphene filler and the high-thermal-conductivity graphene filler in radiation and thermal conductivity cannot be fully exerted, so that the thermal conductivity and the emissivity of the coating are not outstanding, and the heat dissipation effect is poor. In comparative example 7, the overall thermal conductivity of the multi-layer structure coating is significantly lower than that of the gradient coating, which is due to the poor thermal conductivity of the high-emissivity graphene-based coating on the surface layer, and the interface between the two coatings in the double-coating structure further hinders the heat transfer, so the heat dissipation effect of the coating is also poor.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A graphene-based temperature control coating is characterized in that the graphene-based temperature control coating covers a substrate and comprises a heat conduction-radiation seamless series connection heat dissipation gradient structure formed by high heat conduction graphene powder and high radiation graphene powder, wherein the contents of the high heat conduction graphene powder and the high radiation graphene powder are respectively distributed in a gradient manner in the thickness direction of the graphene-based temperature control coating; the mass ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder is changed from 1: 0.01-1: 0.1 to 1: 1-1: 5 in a gradient manner from one side close to the base material to the other side far away from the base material.
2. The graphene-based temperature-control coating of claim 1, wherein the defect density of the high thermal conductivity graphene powder is less than 9 x 10 10 cm -2 。
3. The graphene-based temperature-control coating of claim 1, wherein the defect density of the high-emissivity graphene powder is greater than 4 x 10 12 cm -2 。
4. The graphene-based temperature-controlled coating of claim 1, wherein the thermally conductive-radiative seamless series thermal gradient structure has a longitudinal thermal conductivity greater than 6.5W/(m-K) and an emissivity greater than 0.94.
5. A preparation method of the graphene-based temperature control coating according to any one of claims 1-4, wherein the preparation method comprises the following steps:
s1, providing the high-thermal-conductivity graphene-based composite coating through the high-thermal-conductivity graphene powder, and providing the high-radiation graphene-based composite coating through the high-radiation graphene powder;
s2, dynamically coating the high-thermal-conductivity graphene-based composite coating and the high-radiation graphene-based composite coating on the substrate simultaneously, wherein the loading rate of the high-thermal-conductivity graphene-based composite coating is gradually reduced, the loading rate of the high-radiation graphene-based composite coating is gradually increased, the initial coating loading rate ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder is 1: 0.01-1: 0.1, the final coating loading rate ratio is 1: 1-1: 5, or S2', coating a dynamic mixture of the high-thermal-conductivity graphene-based composite coating and the high-radiation graphene-based composite coating on the substrate, the content of the high-thermal-conductivity graphene-based composite coating in the dynamic mixture is gradually reduced, the content of the high-radiation graphene-based composite coating is gradually increased, the initial mixing loading rate ratio of the high-thermal-conductivity graphene powder to the high-radiation graphene powder is 1: 0.01: 0.1, the final state mixed loading rate ratio is 1: 1-1: 5.
6. The preparation method of the graphene-based composite coating according to claim 5, wherein the composition of the graphene-based composite coating with high thermal conductivity is 1-10% of graphene powder with high thermal conductivity, 40-60% of structural adhesive, 30-60% of dispersion medium and 0.5-5% of auxiliary agent.
7. The preparation method of the graphene-based composite coating, according to claim 5, is characterized in that the high-radiation graphene-based composite coating comprises 1-20% of high-radiation graphene powder, 40-60% of structural adhesive, 20-50% of dispersion medium and 0.5-5% of auxiliary agent.
8. The method according to claim 6 or 7, wherein the structural adhesive is one or more of silicone resin, silicate, ethyl silicate, silica sol, and phosphate.
9. The method for preparing a porous material according to claim 5, wherein the coating in step S2 or S2' is spray coating or spin coating.
10. The method as claimed in claim 5, wherein the substrate in step S2 or S2' is an inorganic non-metal, metal or organic material.
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