WO2022179332A1 - 一种电红外致热膜及其制备方法、电红外致热装置 - Google Patents

一种电红外致热膜及其制备方法、电红外致热装置 Download PDF

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WO2022179332A1
WO2022179332A1 PCT/CN2022/071866 CN2022071866W WO2022179332A1 WO 2022179332 A1 WO2022179332 A1 WO 2022179332A1 CN 2022071866 W CN2022071866 W CN 2022071866W WO 2022179332 A1 WO2022179332 A1 WO 2022179332A1
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infrared heating
electric infrared
heating film
film
electric
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PCT/CN2022/071866
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English (en)
French (fr)
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邵国胜
张鹏
李子轩
陆柳
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郑州新世纪材料基因组工程研究院有限公司
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Priority to JP2023552254A priority Critical patent/JP2024508000A/ja
Priority to EP22758698.9A priority patent/EP4301089A1/en
Publication of WO2022179332A1 publication Critical patent/WO2022179332A1/zh

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/28—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material
    • H05B3/283—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material the insulating material being an inorganic material, e.g. ceramic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H05B3/42—Heating elements having the shape of rods or tubes non-flexible
    • H05B3/44—Heating elements having the shape of rods or tubes non-flexible heating conductor arranged within rods or tubes of insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013—Heaters using resistive films or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/016—Heaters using particular connecting means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/032—Heaters specially adapted for heating by radiation heating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present disclosure relates to an electric infrared heating film, a preparation method thereof, and an electric infrared heating device, belonging to the technical field of electric heating materials.
  • the tube body As the package body (shell), and the heating wire is arranged in the middle.
  • the heat generated by the heating wire needs to be transferred to the inner surface of the casing through the inert gas or vacuum (low density air) encapsulated on the surface of the heating wire, and then transferred to the outer surface of the casing along the diameter of the casing wall to heat the air.
  • the temperature of the outer surface of the shell is lower than that of the inner surface of the shell, and that of the heat transfer medium (encapsulation gas)/inner wall interface is lower than that of the heat transfer medium/heating wire surface interface.
  • electrothermal materials can be plated and packaged on the inner surface of the shell to reduce the heat exchange link in the heat transfer process and improve the heat transfer efficiency and the utilization rate of electric energy.
  • the current electric heating materials are mainly metal/alloy (electric heating wire) materials or carbon materials, and their thermal expansion coefficient is much larger than that of mainstream package shell materials (ceramic, quartz, high boron temperature-resistant glass). After several times of heating and cooling, especially under high temperature conditions, the material stress change caused by the large thermal expansion coefficient difference is likely to cause the heating material to fall off the inner surface of the shell, reducing the service life of the heating equipment.
  • the present disclosure provides an electric infrared heating film, which is mainly composed of the following components in parts by weight: 10-15 parts of low-defect graphene, 5-20 parts of inorganic filler and 5-10 parts of amorphous carbon.
  • the ratio of the intensity of the D peak to the intensity of the G peak is not greater than 1/10, and the molar ratio of carbon to oxygen in the low-defect graphene is not less than 20:1.
  • the Raman spectrum of the low-defect graphene has a 2D peak, and the distance between the 2D peak and the G peak is reduced by ⁇ 5 cm compared with the distance between the 2D peak and the G peak of natural flake graphite -1 .
  • the thermal expansion coefficient of the inorganic filler is less than or equal to 5 ⁇ 10 -7 /K in the operating temperature range of the electric infrared heating film or in the range of 0-600°C.
  • the D50 particle size of the inorganic filler is smaller than the D50 particle size of the low defect graphene.
  • the inorganic filler particle size D50 is less than 1/150 of the low defect graphene D50 particle size.
  • the inorganic filler is any one or any combination of alumina ceramic powder, zirconia ceramic powder, silicon oxide powder, mica powder, and silicon carbide powder filler; D50 of the inorganic filler Particle size ⁇ 100nm.
  • the thickness of the electric infrared heating film is not greater than 100 ⁇ m.
  • the thickness of the electric infrared heating film is 10-30 ⁇ m.
  • the following steps are included: coating a slurry mainly composed of low-defect graphene, an inorganic filler, a film-forming agent and a solvent to form a film, and after volatilizing the solvent, carbonization treatment is performed to obtain; the film-forming The agent is an organic polymer.
  • the organic polymer is polyolefin, polystyrene, polyacrylate polymer, polyethylene oxide, polyvinylidene fluoride, polyimide, polyurethane, polyacrylonitrile, phenolic resin one or any combination.
  • the slurry further includes a graphene dispersant;
  • the graphene dispersant includes a slurry dispersant and a film dispersant;
  • the slurry dispersant is selected from diphenyl ether, C12-C16 alkyl Benzene sulfonate, ethylene oxide, polyethylene glycol, dibasic acid ester, C12-C16 alkyl diphenyl ether monosulfonate, C12-C16 alkyl diphenyl ether disulfonate, C12- One or any combination of C16 alkyl sulfonate and p-C12-C16 alkyl benzene sulfonate;
  • the film dispersant is selected from C12-C16 alkyl diphenyl ether monosulfonate, C12-C16 alkane One or any combination of sulfonate, alkyl polydextrose, propylene oxide, fatty alcohol alkoxylate, hydroxypropy
  • the temperature of the carbonization treatment is 600-1200° C., and the time is not less than 4 hours.
  • the present disclosure also provides an electric infrared heating device, comprising:
  • the electric infrared heating film according to any one of the above is disposed on the inner wall of the electric infrared heating element, and is sealed inside the electric infrared heating element.
  • the electric infrared heating element comprises one of a lamp type electric infrared heating element, a tube type electric infrared heating element or a plate type electric infrared heating element.
  • the present disclosure also provides an electric infrared heating device, comprising:
  • the electric infrared heating film according to any one of the above is arranged on the inner wall of the tube body, and is sealed inside the tube body;
  • the two electrodes are both electrically connected to the electric infrared heating device, and make the electric infrared heating film generate heat when electrified.
  • the tube body is a quartz tube, a ceramic tube or a glass tube.
  • the present disclosure also provides an electric infrared heating device, comprising:
  • the plate-type electric infrared heating element includes a plate body and an electrode; the electric infrared heating film is arranged on the inner wall of the plate body, and the electrode is electrically connected with the electric infrared heating device, and makes the The electric infrared heating film heats up.
  • Fig. 1 is the structural representation of the electric infrared heating device of Example 13;
  • Fig. 2 is the schematic diagram of the cross-section of the electric infrared heating device of embodiment 13, 19, 20;
  • Fig. 3 is the heating curve of heating up to 300 °C of the electric infrared heating device of embodiment and comparative example in Experimental Example 2;
  • FIG. 4 is a schematic structural diagram of an electric infrared heating device according to some embodiments of the disclosure.
  • 1-quartz tube 2-electric infrared heating film, 3-electrode, 4-sealing head, 5-plate body, 51-first substrate, 52-second substrate, 6-concave metal electrode.
  • the term "defective graphene” refers to various defects introduced or retained in the raw material due to graphene's preparation process. Defects appearing in graphene can be divided into three categories: the first category is carbon vacancies and interstitial carbons are carbon atoms on the substitution positions in the sp2 hybridized carbon atoms of graphene missing or existing carbon atoms on the interstitial position with carbon atoms. .
  • the second type of defects are "intrinsic defects", which are composed of carbon atoms on graphene that are not sp2 orbital hybridization. The change in the hybridization form of these carbon atom orbitals is usually due to their own location, or the surrounding carbon six-membered ring.
  • impurity defects also known as "impure defects", which are impurities formed by non-carbon elements at substitution sites, interstitial sites or bonds with carbon atoms outside the (001) plane. These defects are caused by graphene carbon atoms. Caused by covalently bonded non-carbon atoms.
  • low defect graphene generally refers to a graphene material that is substantially free of Type I defects and Type III defects (impurity defects), or a graphene material with relatively few Type I defects and Type III defects.
  • the graphene material may be a graphene material dominated by the second type of defects (intrinsic defects), and substantially free of the first type of defects and the third type of defects or lower.
  • the intrinsic defects of "low-defect graphene” are mainly formed by carbon atoms in the edge states of graphene sheets.
  • “low defect graphene” usually has a sp2 carbon-dominated crystal structure with a high carbon-to-oxygen ratio.
  • the ratio of D peak intensity to G peak intensity is not greater than 1/10.
  • the molar ratio of carbon to non-carbon atoms (eg, heteroatoms such as N, O) in low-defect graphene is greater than or equal to 20:1.
  • the carbon-oxygen molar ratio in low-defect graphene is not less than 20:1.
  • the low-defect graphene may be graphene prepared by a physical expansion method.
  • amorphous carbon refers to those carbon materials that are extremely low-crystallized and belong to an amorphous state (ie, the arrangement of carbon atoms does not possess a long-range periodic ordered structure, also known as a glassy condensed state) , such as carbon black, is a large class of carbon allotropes.
  • natural flake graphite refers to natural crystalline graphite, which is like fish phosphorus, belongs to the hexagonal crystal system, and has a layered structure. Generally, natural flake graphite has good properties such as high temperature resistance, electrical conductivity, thermal conductivity, lubrication, plasticity and acid and alkali resistance.
  • D peak belongs to the Raman characteristic peak of C atomic crystal, and the D-peak represents the defect of C atomic crystal.
  • G-peak belongs to the Raman characteristic peak of C atomic crystal, and the G-peak represents the in-plane stretching vibration of C atom sp2 hybridization.
  • the term "2D peak”, also known as the G* peak, is caused by double-resonant Raman scattering of two-phonon emission, and its appearance is based on the crystal structure of hexagonal crystal planes with long-range ordered sp2 carbon bonds feature.
  • the present disclosure provides an electric infrared heating film with a lower thermal expansion coefficient difference from the packaging shell material, which can significantly prolong the service life of the heating device.
  • the present disclosure also provides a preparation method of the above electric infrared heating film and an electric infrared heating device using the above electric infrared heating film.
  • An embodiment of the present disclosure provides an electric infrared heating film, and the technical solution adopted by the electric infrared heating film is:
  • An electric infrared heating film is mainly composed of the following components in parts by weight: 10-15 parts of low-defect graphene, 5-20 parts of inorganic filler and 5-10 parts of amorphous carbon.
  • the electric infrared heating film can be mainly composed of the following components by weight: the low defect graphene can be, for example, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts , 13.5 parts, 14 parts, 14.5 parts, 15 parts, the inorganic filler can be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, and amorphous carbon can be, for example, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts , 9.5 copies, 10 copies.
  • the use of low-defect graphene can make the electric infrared heating film rapidly heat up to above 300° C. (including 300° C.) and reduce the expansion coefficient of the electric infrared heating film when electrified.
  • the inorganic filler phase Compared with low-defect graphene, it has a lower expansion coefficient, which can reduce the volume expansion coefficient of the electric infrared heating film and the thermal stress generated during rapid heating, while amorphous carbon has elasticity and can buffer low-defect graphene and inorganic fillers.
  • volume expansion further reducing the volume expansion of the electric infrared heating film, thereby narrowing the gap between the volume expansion coefficient of the electric infrared heating film and the base materials such as ceramics, quartz, high boron temperature-resistant glass, etc., to avoid the electric infrared heating film from these materials.
  • the surface falls off, prolonging the service life of the electric infrared heating device.
  • the low thermal expansion characteristic of the inorganic filler in the electric infrared heating film of the present disclosure can improve the integrity of the film during the heating process, and the low-defect graphene can also improve the thermal conductivity of the electric infrared heating film, and then Improve the heat exchange efficiency between the electric infrared heating film and the matrix material, and at the same time, the unique semiconductor electronic structure of low-defect graphene has the ability to emit photons with wavelengths located in the infrared-far-infrared region through the electron relaxation process to heat the target object, and low The pz orbital and sp2- ⁇ orbital of carbon atoms in defective graphene are highly coupled, which can provide good high temperature resistance and good structural stability at high temperature compared with other conductive materials, thereby improving the supply of devices using electric infrared heating films. Higher safety and longer service life.
  • the electric infrared heating film provided by the present disclosure has unique advantages such as small thermal expansion coefficient and fast heat
  • the thermal expansion coefficient of the electric infrared heating film of the present disclosure and the quartz tube have a high degree of matching, and at a temperature rise rate of 50°C/s, the stress generated by the thermal volume expansion difference with the quartz at 800°C is lower than that of the electric infrared heating film.
  • the peel strength of the film greatly increases the upper limit of the heating temperature of the electric infrared heating film.
  • the electric infrared heating film of the present disclosure may also have some impurity components.
  • the ratio of the D peak intensity to the G peak intensity is not greater than 1/10.
  • the ratio of the D peak intensity to the G peak intensity is 1/10, 1/20, 1/30, 1/40, 1/50, 1/60, or 1/70.
  • the defect density of graphene is usually represented by the ratio of the intensity of the D peak to the G peak in the Raman spectrum.
  • the present disclosure can further improve the thermal conductivity of the low-defect graphene heat exchange film by reducing the defect density of the low-defect graphene.
  • the oxygen-to-carbon molar ratio of the low-defect graphene is not more than 1/20 (that is, the carbon-to-oxygen molar ratio in the low-defect graphene is not less than 20:1).
  • low-defect graphene has an oxygen-to-carbon molar ratio of 1/20, 1/30, 1/40, 1/50, 1/60, or 1/70.
  • the present disclosure can ensure that the material has good thermal conductivity and electrical conductivity by controlling the oxygen-to-carbon molar ratio of low-defect graphene within the aforementioned range, and avoid the change of power and heat transfer performance caused by atomic rearrangement of graphene as the main conductive material at high temperature.
  • the thermal conductivity of the infrared heating film can be greater than 200 W/(K ⁇ m) when the thickness is less than 30 ⁇ m.
  • the Raman spectrum of the low-defect graphene has a 2D peak, and the distance between the 2D peak and the G peak is the same as that of the G peak.
  • the distance between them is reduced by more than 5cm -1 , such as reducing 5cm -1 , 8cm -1 , 10cm -1 , 12cm -1 , 14cm -1 , 16cm -1 , 18cm -1 , 18cm -1 , 20cm -1 , 22cm -1 , 24cm -1 , 26cm -1 , 28cm -1 , 30cm -1 , 35cm -1 , 40cm -1 , 45cm -1 or 50cm -1 .
  • the low defect graphene has a D50 particle size of 10-20 ⁇ m, such as 10-15 ⁇ m, 15-20 ⁇ m or 12-18 ⁇ m, eg 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m.
  • the inorganic filler used in the present disclosure has good chemical and structural stability in the working temperature range of the electric infrared heating film.
  • the thermal expansion coefficient of the inorganic filler in the operating temperature range of the electric infrared heating film is below 5 ⁇ 10 -7 /K (including 5 ⁇ 10 -7 /K).
  • the inorganic fillers are alumina ceramic powder, zirconia ceramic powder, silicon oxide powder (ie, silicon dioxide powder), Any one or any combination of mica powder and silicon carbide powder filler.
  • the thermal expansion coefficients of the above-listed inorganic fillers at 0-600°C are below 5 ⁇ 10 -7 /K (including 5 ⁇ 10 -7 /K).
  • the D50 particle size of the inorganic filler is less than the D50 particle size of the low defect graphene, and in some typical embodiments, the inorganic filler particle size D50 is less than 1/150 of the D50 particle size of the low defect graphene.
  • the D50 particle size of the inorganic filler is less than or equal to 100 nm. In some embodiments, the D50 particle size of the inorganic filler is > 20 nm. Since the sheet diameter of graphene as a two-dimensional structural material is much larger than the particle size of the inorganic filler, the inorganic filler and amorphous carbon fill the gap between the graphene sheets after film formation, suppressing the thin film caused by graphene vibration at high temperature The overall stress rises, thereby maintaining the integrity of the graphene composite film at high temperature.
  • the amorphous carbon may be partially or fully formed by carbonization of an organic polymer.
  • the organic polymer includes, but is not limited to, one or any combination of polyolefin, polystyrene, polyacrylate polymer, polyimide, polyurethane, polyvinyl nitrile, and phenolic resin.
  • the polyolefin includes, but is not limited to, one or any combination of polyethylene, polypropylene.
  • the polyvinyl nitrile may be, for example, polyacrylonitrile.
  • the polyacrylate-based polymer may be, for example, polymethyl methacrylate.
  • the thickness of the electric infrared heating film of the present disclosure can be flexibly set according to application scenarios, for example, not greater than 100 ⁇ m. In some embodiments, the thickness of the electric infrared heating film is 10-30 ⁇ m.
  • the electric infrared heating film with a thickness of 10-30 ⁇ m has advantages in use compared with the thicker electric infrared film in the occasions where the heat exchange efficiency of the heating product is required, such as rapid heating equipment.
  • An embodiment of the present disclosure provides a method for preparing an electric infrared heating film, and the technical solution adopted in the method is:
  • a preparation method of the above-mentioned electric infrared heating film comprising the following steps: coating a film-forming slurry mainly composed of low-defect graphene, an inorganic filler, a film-forming agent, a graphene dispersant and a solvent to form a film, volatilizing After the solvent is carbonized, it is obtained; the film-forming agent is an organic polymer.
  • the preparation method of the electric infrared heating film of the present disclosure adopts the method of volatilizing the solvent after the film-forming slurry is applied to shape the coated film, and then the whole film is calcined in a protective atmosphere to promote the carbonization of the film-forming agent in the film into an amorphous form carbon, forming an electric infrared heating film.
  • the method is convenient to control the uniformity of the electric infrared heating film, release the stress in the film and between the film and the substrate, improve the life of the material, improve the heat exchange efficiency of the electric infrared heating film, and is suitable for a series of different high-temperature heating products. reduce manufacturing cost.
  • the mass ratio of the inorganic filler to the low-defect graphene is 5-20:10-15, such as 5-15:10-15, 10-20:11-15 or 15 -20:11-14.
  • the organic polymer is a polymer that can be carbonized into amorphous carbon, such as a resin.
  • the organic polymer film-forming agent is polyolefin, polystyrene, polyacrylate polymer, polyethylene oxide, polyethylene One or any combination of vinylidene fluoride, polyimide, polyurethane, polyacrylonitrile, and phenolic resin.
  • the listed organic polymers are all commercially available conventional polymer resins that can be used for high-temperature carbonization, and have excellent film-forming properties.
  • the polyolefin is one of polyethylene, polypropylene, or any combination.
  • the polyvinyl nitrile is polyacrylonitrile.
  • the polyacrylate polymer is one or any combination of polymethyl methacrylate and polyethyl acrylate.
  • the mass ratio of the film former to the low-defect graphene is 2.6-9.8:4.9-10.4, such as 3.0-9.8:5.0-10.4, 2.6-8.0:5.0-9.0, or 3.5-8.5 : 5.5-7.5.
  • the graphene dispersing agent adopts a material that can promote the dispersion of graphene in the system.
  • a dispersant can be used.
  • the graphene dispersant may include a slurry dispersant.
  • the slurry dispersant can be selected from, for example, diphenyl ether, C12-C16 alkyl benzene sulfonate, ethylene oxide, polyethylene glycol, dibasic acid ester, C12-C16 alkyl diphenyl ether monosulfonic acid Acid salt, C12-C16 alkyl diphenyl ether disulfonate, C12-C16 alkyl sulfonate, p-C12-C16 alkyl benzene sulfonate in any one or a combination.
  • the polyethylene glycol has a molecular weight (M w ) ⁇ 400.
  • the listed slurry dispersants are all conventional compounds available in the market, which can be effectively volatilized during the process of volatilizing the solvent or rarely remain in the formed film and are completely volatilized during carbonization.
  • Low-defect graphene is insoluble in any neutral solvent, and has a low degree of solvation with most solvents.
  • the slurry is The mass ratio of the material dispersant to the low-defect graphene is not less than 1.1:1, for example, 1.1-2.1:1.
  • the dispersant includes a film dispersant.
  • the film dispersant is C12-C16 alkyl diphenyl ether monosulfonate, C12-C16 alkyl sulfonate, alkyl polyglucose, propylene oxide, fatty alcohol One or any combination of alkoxylates, hydroxypropyl methylcellulose and polyvinylpyrrolidone. Since the thin film dispersant with a large number of polar functional groups will release gas during the carbonization process, it may cause damage to the integrity and compactness of the electric infrared heating film.
  • the thin film dispersant The mass of the film-making slurry does not exceed 1%.
  • the mass ratio of the film dispersant after carbonization is negligible compared to the mass ratio of the film-forming agent after carbonization.
  • the listed organic polymers are all commercially available conventional dispersants.
  • the C12-C16 alkyl diphenyl ether monosulfonate is, for example, sodium cetyl diphenyl ether monosulfonate.
  • the C12-C16 alkyl diphenyl ether disulfonate is, for example, sodium cetyl diphenyl ether disulfonate.
  • the p-C12-C16 alkylbenzene sulfonate is, for example, propyl p-toluenesulfonate.
  • the C12-C16 alkyl sulfonate is, for example, sodium cetyl sulfonate.
  • the paste further includes additives; the additives are any one or a combination of a leveling agent, a thickening agent, a thixotropic agent, and a conductive agent.
  • the mass ratio of the additive amount to the low-defect graphene is not more than 1:20.
  • the viscosity of the film-forming slurry is >3000 Pa ⁇ s, and the solid content is >10 wt%. In some embodiments, the solid content of the film-forming slurry is 18.9-25.5%, such as 19%, 20%, 21%, 22%, 23%, 24%, 25%, and the viscosity is 3800-7300 Pa ⁇ s , such as 4000-7300Pa ⁇ s, 3800-7000Pa ⁇ s or 4500-6500Pa ⁇ s, such as 4000Pa ⁇ s, 4500Pa ⁇ s, 5000Pa ⁇ s, 5500Pa ⁇ s, 6000Pa ⁇ s, 6500Pa ⁇ s, 7000Pa ⁇ s, 7200Pa ⁇ s ⁇ s.
  • the D50 particle size of the low-defect graphene in the film-forming slurry is 10-20 ⁇ m.
  • the preparation method of the film-forming slurry includes the following steps: sand-grinding a mixture mainly composed of low-defect graphene powder, inorganic filler, slurry dispersant and part of a solvent, and then adding the mixture to form a film agent, film dispersant and remaining solvent, and mixed.
  • the low-defect graphene can be well dispersed, and the overlapping of the lamellae can be avoided.
  • the low-defect graphene used lacks defects and oxidized functional groups, and the polarization effect with the solvent is poor.
  • Crushing the low-defect graphene raw material, sanding the mixture, and using a dispersant can promote low-defect graphite.
  • the uniform dispersion of graphene in the slurry and the avoidance of sheet stacking ensure that low-defect graphene is presented in the electric infrared heating film in the form of few sheets and a complete structure, thereby further improving the infrared radiation performance of the film.
  • the solvent is methanol, ethanol, n-butanol, propylene glycol, ethyl acetate, toluene, xylene, N-methylpyrrolidone (NMP), acetone, N, One or any combination of N-dimethylformamide, tetrahydrofuran, epoxy reactive diluent, 1,4-butanediol diglycidyl ether.
  • the mass ratio of the solvent to the slurry dispersant in the low-defect graphene is 8-15:1-5, such as 10-15:1-5, 11-15: 1 to 4 or 12 to 15:1 to 3, for example, 2.9 to 9.5:1.
  • the main solvent is selected from one or any combination of N-methylpyrrolidone and ethyl acetate; the dilution solvent is N-methylpyrrolidone.
  • the mass ratio of the dilution solvent to the main solvent is 39-54.8:11.4-22.1, for example, 40-54:11.5-22.0, 39-54:12-20 or 40-52:15-20.
  • the temperature of the carbonization treatment is 600-1200° C., and the time is not less than 4 hours.
  • the temperature before the carbonization treatment, the temperature is first heated to 400° C. for 1 h, and then the temperature is raised to the carbonization treatment temperature to perform the carbonization treatment. The rate of temperature increase was 5°C/min. After the carbonization treatment, the temperature of the carbonization treatment was lowered to 500° C. for 1 h, and then the temperature was lowered. The carbonization treatment is carried out in a protective atmosphere.
  • An embodiment of the present disclosure provides an electric infrared heating device, which includes:
  • any of the above electric infrared heating films is arranged on the inner wall of the electric infrared heating element, and is sealed inside the electric infrared heating element.
  • the electric infrared heating element includes one of a lamp type electric infrared heating element, a tube type electric infrared heating element, or a plate type electric infrared heating element.
  • the electric infrared heating element may be a tubular electric infrared heating element.
  • the tubular electric infrared heating element includes a tubular body.
  • the electric infrared heating device comprises:
  • the tubular electric infrared heating element includes a tube body and an electrode; the electric infrared heating film is arranged on the inner wall of the tube body, and the electrode is electrically connected with the electric infrared heating device, and the electric infrared heating film is heated when energized.
  • An embodiment of the present disclosure provides an electric infrared heating device, and the technical solution adopted by the device is:
  • An electric infrared heating device comprising: a tube body; any one of the above-mentioned electric infrared heating films, arranged on the inner wall of the tube body, and sealed inside the tube body; two electrodes, both connected to The electric infrared heating device is electrically connected, and the electric infrared heating film is heated when the electric infrared heating device is energized.
  • the electric infrared heating device of the present disclosure adopts the above electric infrared heating film with a lower expansion rate, so that the electric infrared heating film and the substrate have a higher degree of matching degree of expansion rate under the condition of electrification, avoiding the electric infrared heating film Comes off from the base body, resulting in a long service life.
  • the electric infrared heating film of the present disclosure is arranged on the inner wall of the tube body (or electric infrared heating element) to achieve rapid temperature rise to high temperature (>300°C), and the electric infrared heating film has a low temperature.
  • Defective graphene, inorganic filler and amorphous carbon are the main components, which can ensure the performance and structural stability of the electric infrared heating device under repeated heating and cooling and high temperature conditions.
  • the electric infrared heating device can give full play to the intrinsic advantages of high infrared emissivity and high thermal conductivity of low-defect graphene material.
  • the inside of the tube body (or electric infrared heating element) is evacuated or filled with inert gas. Evacuating the inside of the tubular (or electric infrared heating element) substrate or filling the tubular substrate with an inert gas can avoid the oxidation of low-defect graphene and amorphous carbon at high temperature.
  • the tube body is one of a quartz tube, a ceramic tube, and a glass tube, such as a quartz tube.
  • a quartz tube is selected as the tube body, the difference in expansion coefficient between the electric infrared heating film of the present disclosure and the quartz is small, and the use of the quartz tube as the substrate can further prolong the service life of the electric infrared heating device.
  • the inner diameter of the tube body is 8-13 mm such as 8 mm, 8.5 mm, 9 mm, 9.5 mm, 10 mm, 10.5 mm, 11 mm, 12 mm, 13 mm.
  • the wall thickness of the tube body is 0.1-2 mm such as 0.2 mm, 0.5 mm, 0.7 mm, 1 mm, 1.5 mm, 1.8 mm, 2 mm.
  • the electric infrared heating element may be a plate electric infrared heating element.
  • the plate electric infrared heating elements include ceramic plate electric infrared heating elements, mica plate electric infrared heating elements, quartz plate electric infrared heating elements, and metal plate electric infrared heating elements with ceramic coating.
  • the electric infrared heating device comprises:
  • the plate-type electric infrared heating element includes a plate body and an electrode; the electric infrared heating film is arranged on the inner wall of the plate body, the electrode is electrically connected with the electric infrared heating device, and the electric infrared heating film is heated when electrified.
  • the plate body includes a first substrate and a second substrate.
  • the first substrate and the second substrate are bonded by means such as hot pressing to form a sealing body; the electric infrared heating film is located on the first substrate on the bonding side of the first substrate and the second substrate, or the first substrate is on two substrates or on both the first substrate and the second substrate.
  • the material of the plate body includes quartz, borosilicate, mica, carbon steel plate with insulating ceramic layer, and aluminum alloy plate with insulating ceramic layer.
  • the preparation of the electric infrared heating device of the present disclosure includes the following steps: coating a slurry mainly composed of low-defect graphene, an inorganic filler, a film-forming agent and a solvent on the inner wall of the tube body to form a film, and volatilizing the solvent After carbonization, the temperature is lowered, and then the electrode is installed and the tube body is sealed.
  • the low-defect graphene used in the present disclosure can either be purchased, or can be prepared according to the method disclosed in the Chinese Published Patent Application No. CN108622887A.
  • the electric infrared heating film of this embodiment is composed of the following components in parts by weight: 5 parts of amorphous carbon, 10 parts of low-defect graphene, and 10 parts of inorganic filler; wherein, the inorganic filler is nano-silica,
  • the D50 particle size is 20 nm; the D50 particle size of low-defect graphene is 15 ⁇ m, the Raman spectrum of low-defect graphite has a 2D peak, and the distance between the 2D peak and the G peak is compared with the distance between the 2D peak and the G peak of natural flake graphite, Reduce by more than 5cm -1 (including 5cm -1 ), and the ratio of D peak intensity to G peak intensity is 1/20, and the carbon-oxygen molar ratio of low-defect graphene is 30:1; the thickness of the electric infrared heating film is 15 ⁇ m.
  • the electric infrared heating films in Examples 2-6 are all composed of amorphous carbon, low-defect graphene and inorganic filler; the Raman spectrum of the low-defect graphene in each example has 2D peaks, and the 2D peaks are the same as Compared with the distance between the 2D peak and the G peak of natural flake graphite, the distance between the G peaks is reduced by more than 5 cm -1 (including 5 cm -1 ), and the ratio of the D peak intensity to the G peak intensity is 1/20, while the low defect graphite
  • the carbon-oxygen molar ratio of graphene is 30:1; the weight fractions of amorphous carbon, low-defect graphene and inorganic filler in each implementation of the medium-electric infrared heating film, as well as the particle size of low-defect graphene, the type of inorganic filler and The D50 particle size and the thickness of the electric infrared heating film are shown in Table 1.
  • the low-defect graphene raw materials used in Examples 7-12 were purchased from Zhengzhou New Materials Technology Co., Ltd. (CP 1002 low-defect graphene fine powder series products), and were graphene prepared by physical expansion method.
  • This low-defect graphene raw material is detected by Raman spectrum, and the Raman spectrum of low-defect graphene has a 2D peak, and the distance between the 2D peak and the G peak is reduced compared with the distance between the 2D peak and the G peak of natural flake graphite. 5cm -1 or more (including 5cm -1 ), and the ratio of D peak intensity to G peak intensity is 1/20, and the molar ratio of carbon to oxygen is 30:1.
  • the preparation method of the electric infrared heating film of this embodiment taking the preparation method of the electric infrared heating film of Example 1 (component ratio, specifications and parameters) as an example, includes the following steps:
  • the low-defect graphene raw material is processed by airflow crushing to obtain low-defect graphene powder
  • the slurry dispersant used is a combination of ethylene oxide and dibasic acid ester (DBE), the mass ratio of ethylene oxide and DBE is 1:2, the main solvent is N-methylpyrrolidone (NMP), and inorganic
  • the filler is nano-silica
  • the film-forming agent is polyacrylonitrile (PAN)
  • the dilution solvent is N-methylpyrrolidone
  • the film dispersant is polyvinylpyrrolidone (PVP K30);
  • the main carbon material used is low-defect graphene.
  • the particle size D50 of the low-defect graphene is 15 ⁇ m, and the particle size D50 of the inorganic filler is 20 nm;
  • the slurry dispersant used accounts for 15% of the quality of the film-making slurry
  • the main solvent used accounts for 44.1% of the film-making slurry quality
  • the low-defect graphene powder and inorganic fillers used account for 44.1% of the film-making slurry quality. 7.4%
  • the film-forming agent used accounts for 3.7% of the film-making slurry
  • the film dispersant used accounts for 0.7% of the film-making slurry
  • the dilution solvent used accounts for 29.1% of the film-making slurry.
  • the solid content of the film slurry was 19.1 wt %
  • the viscosity was 6000 Pa ⁇ s.
  • step 4) Place the quartz tube from which the slurry was poured out in step 3) into a 90° C. blast oven, and then rotate the quartz tube coaxially in the same direction at a speed of 4 rev/min for 30 min until the inner wall of the tube is shaped into the slurry;
  • Examples 8-12 correspond to the preparation methods of the electric infrared heating films of Examples 2-6 respectively (component ratio, specifications and parameters), and the preparation methods of the electric infrared heating films of Examples 8-12 refer to those of Example 7.
  • the preparation method of the electric infrared heating film, the composition of the film-making slurry prepared in each example is shown in Table 2 and Table 3, the solid content and viscosity of the obtained film-making slurry, the pipe body used and the inner diameter of the pipe body Table 4 shows the thickness and wall thickness and the thickness of the obtained electric infrared heating film, and the parts not mentioned in Tables 2-4 are the same as the preparation method of the electric infrared heating film of Example 7.
  • Table 3 Composition of the film-forming slurry in the preparation method of the electric infrared heating film of Examples 10-12
  • Table 4 The solid content and viscosity of the film-forming slurry, the pipe body used, the inner diameter and wall thickness of the pipe body, and the thickness of the obtained electric infrared heating film in the preparation method of the electric infrared heating film of Examples 8-12
  • the quartz tube in the preparation method of the electric infrared heating film of the embodiment 9 and the embodiment 12 can also be replaced with a ceramic tube, and the preparation method of the embodiment 11 can also be replaced by a ceramic tube.
  • the quartz tube in the method was replaced with a glass tube.
  • the electric infrared heating device of Example 13 is shown in Figures 1-2, including a quartz tube 1, an electric infrared heating film 2, two lead-out electrodes 3, and two sealing heads 4; wherein the electric infrared heating film 2 adopts The electric infrared heating film prepared by the preparation method of Example 7 is coated on the inner wall of the quartz tube 1, and the two lead-out electrodes 3 are respectively nested in the quartz tube 1 at both ends of the quartz tube 1 and placed on the quartz tube 1 respectively.
  • the two ends of 1 are electrically connected with the electric infrared heating film 2; the two sealing heads 4 are respectively located at both ends of the quartz tube 1 and form a seal on the quartz tube 1, and the two lead-out electrodes 3 and the electric infrared heating film 2 are located in the quartz tube 1.
  • the two sealing heads 4 are respectively provided with wire-threading holes for passing the wires electrically connected to the lead-out electrodes at the corresponding ends.
  • the difference between the electric infrared heating device of this embodiment and the electric infrared heating device of embodiment 13 is only that the electric infrared heating film on the inner wall of the quartz tube is the electric infrared heating film prepared by the preparation method of embodiment 8.
  • the difference between the electric infrared heating device of this embodiment and the electric infrared heating device of embodiment 13 is only that the electric infrared heating film on the inner wall of the quartz tube is the electric infrared heating film prepared by the preparation method of embodiment 9.
  • the difference between the electric infrared heating device of this embodiment and the electric infrared heating device of embodiment 13 is only that the electric infrared heating film on the inner wall of the quartz tube is the electric infrared heating film prepared by the preparation method of embodiment 10.
  • the difference between the electric infrared heating device of this embodiment and the electric infrared heating device of embodiment 13 is only that the electric infrared heating film on the inner wall of the quartz tube is the electric infrared heating film prepared by the preparation method of embodiment 11.
  • the difference between the electric infrared heating device of this embodiment and the electric infrared heating device of embodiment 13 is only that the electric infrared heating film on the inner wall of the quartz tube is the electric infrared heating film prepared by the preparation method of embodiment 12.
  • the lead wire is welded to the lead-out electrode, and then the quartz
  • the nano-silver glue is coated on the electric infrared heating film at both ends of the tube, and then the two lead-out electrodes are respectively placed in the quartz tube from both ends of the quartz tube, and the position where the nano-silver glue is coated on the electric infrared heating film is connected with the electric infrared heating.
  • the membrane is attached and fixed, and then the sealing heads are installed on both ends of the quartz tube in a high-purity argon atmosphere, and the lead wires are drawn out through the reserved threading holes on the sealing heads at the corresponding ends.
  • the gap between the sealing head and the quartz tube is sealed.
  • the electric infrared heating device of this embodiment only replaces the quartz tube in the electric infrared device of embodiment 13 with a ceramic tube, and the high-temperature glass tube has only one end of the sealing head with threading holes, and the number of threading holes is two , which are used for the wires that are electrically connected to the two lead-out electrodes to pass through respectively.
  • the dense quartz tube in the electric infrared heating device of Embodiment 18 is replaced by a high temperature glass tube and the sealing head is replaced by a thermoplastic seal, which will not be repeated here.
  • the electric infrared heating device of this embodiment includes a plate body 5 , an electric infrared heating film 2 , and a concave metal electrode 6 ; wherein the plate body 5 includes a first substrate 51 and a second substrate 52 .
  • the first substrate 51 and the second substrate 52 are of the same material and structure, and both are made of quartz.
  • the electric infrared heating film 2 is coated on the surface of the second substrate 52 with the film-forming slurry prepared by the preparation method in steps 1) to 2) of Example 7, and is kept at 50° C. until the second substrate is fixed.
  • the slurry on it does not flow out within 1min, and then the second substrate 52 coated with the electric infrared heating film 2 is placed in a 90°C blast oven for 30min until the second substrate 52 is sizing on the wall.
  • the material is shaped, and according to steps 5) to 6) of Example 7, an electric infrared heating film with a thickness of 25 ⁇ m is formed on the second substrate 52 .
  • the two concave-shaped metal electrodes 6 are respectively fixed on both ends of the electric infrared heating film 2, connected with the electric infrared heating film 2 and sealed and nested between the first substrate 51 and the second substrate 52.
  • the concave-shaped metal electrodes The two arms of 6 are exposed to the outside of the board as electrodes for wiring. Then, the first substrate 51 is covered on the surface of the second substrate 52 coated with the electric infrared heating film 2, and is closely attached by hot-pressing packaging to form a tightly attached sealed space (the concave-shaped metal electrode 6 is selected to reduce seal stress and leak points).
  • the electric infrared heating device of this embodiment is the same as that of embodiment 21.
  • the difference is that the board body 5 is made of high borosilicate material and is packaged by hot pressing.
  • the electric infrared heating device of this embodiment is the same as that of embodiment 21.
  • the difference is that the board body 5 is made of mica material and is packaged by a high temperature resistant adhesive.
  • the electric infrared heating device of this embodiment is the same as that of embodiment 21.
  • the difference is that the plate body 5 is made of carbon steel plate with an insulating ceramic layer, and the insulating layer is inside, and the carbon steel material is outside. Encapsulation with high temperature resistant adhesive.
  • the electric infrared heating device of this embodiment is the same as that of embodiment 21.
  • the difference is that the plate body 5 is made of an aluminum alloy plate with an insulating ceramic layer, and the insulating layer is inside, and the aluminum alloy material is outside. Encapsulation with high temperature resistant adhesive.
  • the redox graphene used in the comparative example is the redox graphene prepared by the HUMMER method, which has a large number of defects.
  • the electric infrared heating devices of Comparative Examples 1-6 differ from the electric infrared heating device of Example 13 only in the electric infrared heating film on the quartz tube.
  • the electric infrared heating film on the inner wall of the quartz tube of Comparative Examples 1-6 was prepared with reference to the preparation method of the electric infrared heating film in Example 7.
  • Comparative Examples 2-6 in order to ensure that a 15 ⁇ m thick electric infrared heating film can be uniformly coated inside the quartz tube, the addition ratio (solid content) of the dilution solvent was adjusted.
  • the main carbon material and solid content, the sanding line speed and the number of cycles, the thickness of the prepared electric infrared heating film, and the mass ratio of the main carbon material, filler and amorphous carbon in the electric infrared heating film are shown in Table 5. The content not mentioned is completely the same as that of Example 7.
  • Table 5 Composition, thickness and preparation method of the electric infrared heating film on the inner wall of the quartz tube of the electric infrared heating device of comparative examples 1-6
  • the redox graphene on the market used in the comparative example has a high defect concentration, and the graphene sheet diameter prepared by the redox method is generally small, and the degree of solvation in the slurry is high.
  • the consistency of the slurry of redox graphene on the market is significantly increased, and the fluidity is significantly decreased, and the method mentioned in step 4) (step 4 of embodiment 7) cannot be adopted. or other means to achieve uniform coating within the tube.
  • the repaired graphene oxide material can further reduce the degree of solvation due to the reduction of defects on the (110) surface. , so the solid content of the slurry can be significantly increased. Similarly, due to the large specific surface area and high degree of solvation of carbon nanotubes and nanocarbon microspheres, the solid content cannot be increased either. Therefore, in Comparative Examples 2-6, the method of reducing the solid content was used to prepare the slurry. However, blindly reducing the solid content of the slurry to improve the fluidity of the slurry not only reduces the viscosity (not the consistency) of the slurry, which is not conducive to the stable adhesion of the slurry in the smooth pipe wall (Comparative Example 2), but also makes the coating slurry easy to apply. During the drying process, due to the evaporation of a large amount of solvent, the internal structure of the dry film is loosened and pinholes appear, which is not conducive to the film-forming property of the material after drying.
  • the electric infrared heating devices of Examples 13, 16, 18 and Comparative Examples 4 to 6 were subjected to repeated heating tests at a constant power of 180 W. After constant temperature, the holding time was 15 minutes. After cooling to below 26 °C, the test was performed again, and the temperature was raised to The number of times that the constant temperature temperature is maintained is 10 times.
  • the effective heating area of each electric infrared heating device, the constant temperature, the time to heat up to the constant temperature and the state of the electric infrared heating device after repeated heating are shown in Table 7; The heating curve of the infrared heating device is shown in Figure 3.
  • the electric infrared heating films prepared in the examples of the present disclosure have higher surface temperature and excellent durability.
  • the high solid content ratio of low-defect graphene in the electric heating film material reflects the high durability of the electric infrared heating film of the present disclosure in repeated heating tests.
  • the conductive loop consists of the main carbon material-main carbon material and the main carbon material-amorphous carbon through physical contact to achieve electrical conduction.
  • the commercial graphene used in Comparative Example 4 has high defects and poor thermal stability. Even under the protection of high-purity inert gas, the high-temperature energization condition will still cause its structural rearrangement, resulting in the occurrence of redox graphene materials. The irreversible structural damage causes its resistance to rise continuously and affects its service life. Although the graphene used in Comparative Example 4 removes most of the third type of defects by a high temperature method, the first type of defects is difficult to repair by this process. Therefore, it does not satisfy the requirement (c) above.
  • the carbon nanotubes in Comparative Example 5 have good structural stability and have a structurally stable effect on the electric infrared heating film, due to their structural reasons, their dispersibility is poor, and it is difficult to increase the solid content ratio. It is difficult to reduce the solvent content. effect on film formation.
  • its one-dimensional electrical and thermal conductivity makes the thermal conductivity of carbon nanotubes relatively low along the wall diameter after film formation.
  • Super-P in Comparative Example 6 has good three-dimensional electrical and thermal conductivity as carbon nanospheres, it is more susceptible to Brownian motion and thermal expansion stress during the heating process due to the point contact with other materials, which makes it a three-dimensional structure.
  • the conductive network is partially damaged, which is not conducive to maintaining the overall electrothermal performance of the electric infrared heating film under working conditions.
  • the super-P used in Comparative Example 6 is nano-carbon microspheres, which is difficult to meet the requirements of (b). Therefore, after several times of heating and cooling, the contact between the main carbon material and the main carbon material will cause the local temperature to be too high and discharge due to the short circuit of thermal expansion and cold contraction, resulting in film cracking.
  • the commercially available heating tubes that can be purchased as high-temperature air heat sources (rated power ⁇ 400W, operating temperature ⁇ 300 °C, and can be burned in empty) are all assembled by using heating wires to pass through the central axis of the tube body.
  • the rated power of the heat pipe is 400W (the heating body is a helical alloy heating wire)
  • the rated power of the commercially available lightwave furnace heating tube is 400W (the heating body is a straightened carbon fiber heating wire)
  • the rated power of the commercially available carbon fiber heating tube is 800W (the heating body is Straightened carbon fiber)
  • the rated power of the commercially available metal wire short-wave infrared heating tube is 500W (the heating body is a straightened alloy heating wire).
  • the heating tube was heated with constant power, and the temperature sampling interval was 7.5 Hz. It took time for the surface of the test tube to heat up to 300 °C, and the power density was calculated. The results are shown in Table 8.
  • the electric infrared heating device of the embodiment compared with the heating pipe of the comparative example, under the same power or lower power/power density, the tube body of the electric infrared heating device of the embodiment in an open environment.
  • the surface heating rate has a significant advantage.
  • the electric infrared heating device of the present disclosure has a significant improvement in electric energy utilization rate, heat transfer and heating efficiency.
  • the heating body has the smallest volume, the outer contour is the farthest from the tube body, and the heating speed is the slowest, which reflects the heating performance advantage brought by the electric infrared heating device of the present disclosure.
  • the infrared conversion rate of the electric infrared heating device of the embodiment reaches more than 75%, and the heating body is close to the outer wall of the heating device. Therefore, it is judged that its heat exchange mechanism is: mainly radiation heat exchange, with The heat conduction method is supplemented.
  • the temperature of the outer wall of the device comes directly from the heating film, and there is no convective heat transfer and the heat transfer mechanism of the heating body-internal environment-tube wall.
  • the electric infrared conversion rate of the electric infrared heating device of the embodiment still has a lower average power (400-500W) than half of the commercially available heating tubes. >75% IR radiation conversion rate, which is due to its superior IR radiation performance largely due to the additional IR radiation ability of low-defect graphene and the superior material mechanical properties of the electric infrared heating film at high temperature. It is brought about by the design of seamless heat transfer with the tube wall.
  • Examples 13, 16 and 18 are only used as an exemplary illustration for comparison with the comparative example, and cannot limit the scope of the present disclosure and the claims.
  • 15, 17, 19-20 and the electric infrared heating devices prepared in other embodiments also have technical effects similar to those of Examples 13, 16 and 18 in all the experimental effects related to the above-mentioned experimental examples.
  • the probability of separation of the electric infrared heating film and the inner wall of the device is reduced, thereby ensuring the structure of the electric infrared heating device. and performance stability.
  • low-defect graphene, inorganic fillers, and amorphous carbon can reduce the volume expansion coefficient of the electric infrared heating film, and reduce the temperature resistance of the electric infrared heating film and ceramics, quartz, and high boron.
  • the heating device has excellent application value.

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Abstract

一种电红外致热膜及其制备方法、电红外致热装置，属于电加热材料技术领域。电红外致热膜，主要由以下重量份数的组分组成：低缺陷石墨烯10～15份、无机填充剂5～20份和无定型碳5～10份。电红外致热膜中的低缺陷石墨烯、无机填充剂、无定型碳能够降低电红外致热膜的体积膨胀系数，缩小电红外致热膜与陶瓷、石英、高硼耐温玻璃等基体材料的体积膨胀系数的差距，避免电红外致热膜从这些材料表面脱落，延长电红外致热装置的使用寿命。

Description

一种电红外致热膜及其制备方法、电红外致热装置
相关申请的交叉引用
本公开要求于2021年02月26日提交中国专利局的申请号为“CN 202110220155.6”名称为“一种电红外致热膜及其制备方法、电红外致热装置”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及一种电红外致热膜及其制备方法、电红外致热装置，属于电加热材料技术领域。
背景技术
目前作为空气热源的高温加热管产品大多采用管体为封装体(壳体)，中间布设加热丝，通电升温后依靠惰性气体传热，并透过石英/陶瓷/金属管进行辐射发光发热。通电后加热丝产生的热量需通过电热丝表面加热封装的惰性气体或真空(低密度空气)传至壳体内表面后再沿壳体壁径方向传至壳体外表面对空气进行加热。根据热力学第一定律，壳体外表面温度低于壳体内表面低于传热介质(封装气体)/内壁介面低于传热介质/加热丝表面介面。造成传热速度低下，电能利用率低下等缺点。为了解决这个问题，可将电热材料镀覆与封装壳体内表面，减少热传递过程中换热环节，提高传热效率与电能利用率。
然而，目前电加热材料主要为金属/合金(电热丝)材料或碳素材料，其热膨胀系数远大于主流封装壳体材料(陶瓷、石英、高硼耐温玻璃)。多次升降温后，尤其是高温工况下，较大的热膨胀系数差导致的材料应力变化容易造成加热材料从壳体内表面脱落，降低加热设备的使用寿命。
发明内容
本公开提供一种电红外致热膜，主要由以下重量份数的组分组成：低缺陷石墨烯10～15份、无机填充剂5～20份和无定型碳5～10份。
在一些实施方式中，所述低缺陷石墨烯的拉曼光谱图中，D峰强度与G峰强度之比不大于1/10，且低缺陷石墨烯中碳氧摩尔比不小于20:1。
在一些实施方式中，所述低缺陷石墨烯的拉曼光谱图中具有2D峰，且所述2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少≥5cm -1。
在一些实施方式中，所述无机填充剂在电红外制热膜的工况温度区间或在0-600℃范围内的热膨胀系数≤5×10 -7/K。
在一些实施方式中，所述无机填充剂的D50粒度小于所述低缺陷石墨烯的D50粒度。
在一些实施方式中，所述无机填充剂粒度D50小于所述低缺陷石墨烯D50粒度的1/150。
在一些实施方式中，所述无机填充剂为氧化铝陶瓷粉、氧化锆陶瓷粉、氧化硅粉体、云母粉、碳化硅粉填料中的任意一种或任意组合；所述无机填充剂的D50粒度≤100nm。
在一些实施方式中，所述电红外致热膜的厚度不大于100μm。
在一些实施方式中，所述电红外致热膜的厚度为10～30μm。
在一些实施方式中，包括以下步骤：将主要由低缺陷石墨烯、无机填充剂、成膜剂和溶剂组成的浆料涂覆成膜，挥发溶剂后进行碳化处理，即得；所述成膜剂为有机聚合物。
在一些实施方式中，所述有机聚合物为聚烯烃、聚苯乙烯、聚丙烯酸酯类聚合物、聚氧化乙烯、聚偏氟乙烯、聚酰亚胺、聚氨酯、聚丙烯腈、酚醛树脂中的一种或任意组合。
在一些实施方式中，所述浆料还包括石墨烯分散剂；所述石墨烯分散剂包括浆料分散剂和薄膜分散剂；所述浆料分散剂选自二苯醚、C12-C16烷基苯磺酸酯、环氧乙烷、聚乙二醇、二元酸酯、C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基二苯基醚二磺酸盐、C12-C16烷基磺酸盐、对C12-C16烷基苯磺酸酯中的一种或任意组合；所述薄膜分散剂选自C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基磺酸盐、烷基多聚葡萄糖、环氧丙烷、脂肪醇烷氧基化物、羟丙基甲基纤维素、聚乙烯吡咯烷酮中的一种或任意组合。
在一些实施方式中，所述碳化处理的温度为600～1200℃，时间不少于4h。
本公开还提供一种电红外致热装置，包括：
电红外加热元件；
如上文任意一项所述的电红外致热膜，设置于所述电红外加热元件的内壁上，并被密封于所述电红外加热元件内部。
在一些实施方式中，所述电红外加热元件包括灯式电红外加热元件、管式电红外加热元件或板式电红外加热元件的一种。
本公开还提供一种电红外致热装置，包括：
管体；
如上文任意一项所述的电红外致热膜，设置于所述管体的内壁上，并被密封于所述管体内部；
两个电极，均与所述电红外致热装置电连接，并在通电时使电红外致热膜发热。
在一些实施方式中，所述的管体为石英管、陶瓷管或玻璃管。
本公开还提供一种电红外致热装置，包括：
板式电红外加热元件；
如上文中任意一项所述的电红外致热膜；
所述板式电红外加热元件包括板体和电极；所述电红外致热膜设置于所述板体的内壁上，所述电极与所述电红外致热装置电连接，并在通电时使所述电红外致热膜发热。
附图说明
图1为实施例13电红外致热装置的结构示意图；
图2为实施例13、19、20的电红外致热装置横截面的示意图；
图3为实验例2中实施例和对比例的电红外致热装置的升温至300℃的升温曲线；
图4为本公开一些实施方式的电红外致热装置的结构示意图；
其中，1-石英管，2-电红外制热膜，3-电极，4-密封头，5-板体，51-第一基板，52-第二基板，6-凹字形金属电极。
术语定义
在利用实施方式和实施例描述本发明之前，应理解本文所用术语仅用于描述特定实施方式和实施例的目的，并不旨在限制本发明的范围。
如本文所用，术语“缺陷石墨烯”是指由于石墨烯在制备过程中，引入或保留了原料中的各种缺陷。石墨烯中出现的缺陷可分为三类：第一类为碳空位与间隙碳为在石墨烯sp2杂化的碳原子中取代位上的碳原子缺失或存在与碳原子间隙位上的碳原子。第二类缺陷为“本征缺陷”，由石墨烯上非sp2轨道杂化的碳原子组成，这些碳原子轨道杂化形式的变化，通常是因为本身所在的，或者周围的碳六元环中缺少或者多出碳原子所导致。典型地，本征缺陷是由于石墨烯片径有限在边缘处具有未成键电子，由石墨烯上非sp2轨道杂化的碳原子形成。第三类缺陷为杂质缺陷，也称为“不纯缺陷”，由非碳元素在取代位、间隙位或与碳原子在(001)面外成键的杂质，这些缺陷是由与石墨烯碳原子共价结合的非碳原子导致的。诸如在化学方法还原氧化石墨法中，由于氧化石墨烯在制备过程中引入大量的含氧官能团，造成sp2碳晶格结构严重破坏，由其制得的石墨烯往往包含大量含氧官能团有关的杂质缺陷及碳sp2晶格无序化缺陷。在本文中，“低缺陷石墨烯”通常指基本没有第一类缺陷和第三类缺陷(杂质缺陷)的石墨烯材料，或第一类缺陷和第三类缺陷较低的石墨烯材料。典型地，石墨烯材料可以是以第二类缺陷(本征缺陷)为主的石墨烯材料，基本没有第一类缺陷和第三类缺陷或较低。典型地，“低缺陷石墨烯”本征缺陷主要为石墨烯片层边缘态碳原子形成。典型地，“低缺陷石墨烯”通常具有sp2碳为主的晶体结构，具有碳氧比高的特性。典型地，低缺陷石墨烯的拉曼光谱图中，D峰强度与G峰强度之比不大于1/10。典型地，低缺陷石墨烯中碳与非碳原子(例如杂原子，诸如N、O)摩尔比大于等于20:1。例如，低缺陷石墨烯中碳氧摩尔比不小于20:1。例如，低缺陷石墨烯可以是物理膨爆法制备的石墨烯。
如本文所用，术语“无定形碳”是指那些结晶化程度极低，属于非晶体状态(即碳原子排布不具备长程周期性有序结构，又称为玻璃态的凝聚态)的碳材料，如炭黑等，是碳的同素异形体中的一大类。
如本文所用，术语“天然鳞片石墨”是指天然显晶质石墨，其形似鱼磷状，属六方晶系，呈层状结构。通常，天然鳞片石墨具有良好的耐高温、导电、导热、润滑、可塑及耐酸碱等性能。
如本文所用，术语“D峰”属于C原子晶体的拉曼特征峰，D-峰代表的是C原子晶的缺陷。
如本文所用，术语“G峰”属于C原子晶体的拉曼特征峰，G-峰代表的是C原子sp2杂化的面内伸缩振动。
如本文所用，术语“2D峰”又称为G*峰，由双声子发射的双共振拉曼散射引起，其出现的基础条件，是具有长程有序sp2碳键组成的六角晶面的晶体结构特征。
具体实施方式
本公开提供一种与封装壳体材料之间具有较低热膨胀系数差异的电红外致热膜，能够显著延长加热设备的使用寿命。
本公开还提供了一种上述电红外致热膜的制备方法以及一种采用上述电红外致热膜的电红外致热装置。
本公开一实施方式提供一种电红外致热膜，该电红外致热膜采用的技术方案是：
一种电红外致热膜，主要由以下重量份数的组分组成：低缺陷石墨烯10～15份、无机填充剂5～20份和无定型碳5～10份。在一些实施方式中，电红外致热膜主要可以由以下重量份数的组分组成：低缺陷石墨烯可以为例如10份、10.5份、11份、11.5份、12份、 12.5份、13份、13.5份、14份、14.5份、15份，无机填充剂可以为例如5份、6份、7份、8份、9份、10份、11份、12份、13份、14份、15份、16份、17份、18份、19份、20份，以及无定型碳可以为例如5份、5.5份、6份、6.5份、7份、7.5份、8份、8.5份、9份、9.5份、10份。
本公开的电红外致热膜，采用低缺陷石墨烯能够使电红外致热膜在通电时快速升温至300℃以上(包括300℃)并降低电红外致热膜的膨胀系数，无机填充剂相较于低缺陷石墨烯具有更低的膨胀系数，能够降低电红外致热膜的体积膨胀系数以及快速升温时产生的热应力，而无定型碳具有弹性能够缓冲低缺陷石墨烯以及无机填充剂的体积膨胀，进一步降低电红外致热膜的体积膨胀，从而缩小电红外致热膜与陶瓷、石英、高硼耐温玻璃等基体材料的体积膨胀系数的差距，避免电红外致热膜从这些材料表面脱落，延长采用电红外致热装置的使用寿命。
此外，本公开的电红外致热膜中的无机填充剂具有的低热膨胀特性可以提高的发热过程中膜的完整性，而低缺陷石墨烯还能提高电红外致热膜的热导率，进而提高电红外致热膜与基体材料的换热效率，同时低缺陷石墨烯特有的半导体电子结构具有通过电子弛豫过程发射波长位于红外-远红外区域的光子辐照加热目标物体的能力，并且低缺陷石墨烯中碳原子的pz轨道与sp2-σ轨道高度耦合，与其他导电材料相比可以提供良好的耐高温能力、高温下良好的结构稳定性，从而提高供给采用电红外致热膜的器件更高的安全性、更长的使用寿命。与传统高温电加热材料相比，本公开提供的电红外致热膜具有热膨胀系数小、导热快等独特优势。
本公开电红外致热膜与石英管的热膨胀系数具有较高的匹配程度，在50℃/s的温升速率下，在800℃下与石英热体积膨胀差产生的应力低于电红外致热膜的剥离强度，大大提高了电红外致热膜的发热温度上限。
可以理解的是本公开的电红外制热膜中除低缺陷石墨烯、无定性碳以及无机填充剂外还有可能具有一些杂质成分。
为了进一步提高电红外致热膜的导热性能，所述低缺陷石墨烯的拉曼光谱图中，D峰强度与G峰强度之比不大于1/10。例如，D峰强度与G峰强度之比为1/10、1/20、1/30、1/40、1/50、1/60或1/70。通常以拉曼光谱图中的D峰与G峰的强度之比来表示石墨烯的缺陷密度，本公开通过降低低缺陷石墨烯的缺陷密度能够进一步提高低缺陷石墨烯换热膜的导热性能。所述低缺陷石墨烯的氧碳摩尔比不大于1/20(即低缺陷石墨烯中碳氧摩尔比不小于20:1)。例如，低缺陷石墨烯的氧碳摩尔比为1/20、1/30、1/40、1/50、1/60或1/70。本公开通过控制低缺陷石墨烯的氧碳摩尔比在前述范围可以确保材料具有良好的导热性和导电性，避免高温下石墨烯作为主要导电材料发生原子重排导致功率和换热性能发生变化。本公开通过降低采用的低缺陷石墨烯的缺陷浓度，可以使红外致热膜在厚度低于30μm时，导热系数大于200W/(K·m)。为进一步确保其低缺陷石墨烯的稳定性以及导热率等热力学特性，在一些典型的实施方式中，所述低缺陷石墨烯的拉曼光谱图具有2D峰，且2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少5cm -1以上，诸如减少5cm -1、8cm -1、10cm -1、12cm -1、14cm -1、16cm -1、18cm -1、20cm -1、22cm -1、24cm -1、26cm -1、28cm -1、30cm -1、35cm -1、40cm -1、45cm -1或50cm -1。
在一些实施方式中，所述低缺陷石墨烯的D50粒度为10～20μm，诸如10～15μm、15～20μm或12～18μm、例如10μm、12μm、14μm、16μm、18μm、20μm。
本公开采用的无机填充剂在电红外制热膜的工况温度区间具有良好的化学和结构稳定性。在一些典型的实施方式中，所述无机填充剂在电红外制热膜的工况温度区间的热膨胀系数在5×10 -7/K以下(包括5×10 -7/K)。
从成本、浆料分散性、电红外致热膜的结构稳定性方面综合考虑，所述无机填充剂为氧化铝陶瓷粉、氧化锆陶瓷粉、氧化硅粉体(即二氧化硅粉体)、云母粉、碳化硅粉填料中的任意一种或任意组合。上述列举的无机填充剂在0-600℃的热膨胀系数在5×10 -7/K以下(包括5×10 -7/K)。
在一些典型的实施方式中，所述无机填充剂的D50粒度小于低缺陷石墨烯的D50粒度，在一些典型的实施方式中，无机填充剂粒度D50小于低缺陷石墨烯D50粒度的1/150。
为了进一步降低电红外致热膜的膨胀系数，在一些典型的实施方式中，所述无机填充剂的D50粒度≤100nm。在一些实施方式中，所述无机填充剂的D50粒度≥20nm。由于石墨烯作为二维结构材料的片径远远大于无机填充剂的粒径，成膜后无机填充剂与无定型碳填充石墨烯片间的间隙，抑制由于在高温下石墨烯振动造成的薄膜整体应力上升，从而维持石墨烯复合薄膜在高温下的完整性。
在一些实施方式中，所述无定型碳可以部分或全部由有机聚合物碳化形成。在一些实施方式中，所述有机聚合物包括但不限于聚烯烃、聚苯乙烯、聚丙烯酸酯类聚合物、聚酰亚胺、聚氨酯、聚烯腈、酚醛树脂中的一种或任意组合。在一些实施方式中，所述聚烯烃包括但不限于聚乙烯、聚丙烯中的一种或任意组合。所述聚烯腈可以为例如聚丙烯腈。所述聚丙烯酸酯类聚合物可以为例如聚甲基丙烯酸甲酯。
本公开的电红外致热膜的厚度可根据应用场景灵活设置，例如不大于100μm。在一些实施方式中，所述电红外致热膜的厚度为10～30μm。厚度为10～30μm的电红外致热膜在速热设备等对加热产品的换热效率有要求的场合相较于更厚的电红外制膜则有使用上的优势。
本公开一实施方式提供电红外致热膜的制备方法，该方法所采用的技术方案为：
一种上述电红外致热膜的制备方法，包括以下步骤：将主要由低缺陷石墨烯、无机填充剂、成膜剂、石墨烯分散剂和溶剂组成的制膜浆料涂覆成膜，挥发溶剂后进行碳化处理，即得；所述成膜剂为有机聚合物。
本公开的电红外致热膜的制备方法，采用成膜浆料涂敷后挥发溶剂的方式为涂覆薄膜定型，然后对薄膜整体进行保护性气氛煅烧，促进薄膜内成膜剂碳化成无定型碳，形成电红外制热膜。该方法便于控制电红外致热膜的均一性、便于释放薄膜内和薄膜与基材间的应力提高材料寿命、提高电红外致热膜的换热效率，适用于一系列不同高温加热产品，并降低生产成本。
在一些典型的实施方式中，所述无机填充剂与所述低缺陷石墨烯的质量比为5-20:10-15，例如5-15:10-15、10-20:11-15或15-20:11-14。
所述有机聚合物为可经过碳化处理成无定性碳的聚合物，例如树脂。为了提高上述制膜浆料的成膜性能，降低生产成本，在一些实施方式中，所述有机聚合物成膜剂为聚烯烃、聚苯乙烯、聚丙烯酸酯类聚合物、聚氧化乙烯、聚偏氟乙烯、聚酰亚胺、聚氨酯、聚丙烯腈、酚醛树脂中的一种或任意组合。所述列举的有机聚合物均为市售常规的可用于高温碳化的高分子树脂，成膜性能优良。在一些实施方式中，所述聚烯烃为聚乙烯、聚丙烯中的一种或任意组合。所述聚烯腈为聚丙烯腈。所述聚丙烯酸酯类聚合物为聚甲基丙烯酸甲酯、聚丙烯酸乙酯中的一种或任意组合。
在一些典型的实施方式中，所述成膜剂与低缺陷石墨烯的质量比为2.6-9.8:4.9-10.4，例如3.0-9.8:5.0-10.4、2.6-8.0:5.0-9.0或3.5-8.5:5.5-7.5。
为确保上述制膜浆料在低温固化成膜过程中低缺陷石墨烯组分分散良好、与成膜剂在浆料成膜后均匀分布，石墨烯分散剂采用能够促进石墨烯在体系中分散的分散剂即可采用。为提高上述制膜浆料中的低缺陷石墨烯分散性能，并保障浆料涂覆后材料的均一性，所述石墨烯分散剂可以包括浆料分散剂。所述浆料分散剂可以选自例如二苯醚、C12-C16烷基苯磺酸酯、环氧乙烷、聚乙二醇、二元酸酯、C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基二苯基醚二磺酸盐、C12-C16烷基磺酸盐、对C12-C16烷基苯磺酸酯中的任意一种或多种组合。在一些典型的实施方式中，所述聚乙二醇的分子量(M w)＜400。所述列举的浆料分散剂均为市售常规的化合物，在挥发溶剂的过程中可有效挥发或极少残留于成型薄膜中并在碳化时挥发完毕。低缺陷石墨烯不溶于任何中性溶剂，且与绝大多数溶剂溶剂化程度低，为进一步保障低缺陷石墨烯粉体在制膜浆料中能够充分均一地分散，在一些实施方式中，浆料分散剂与所述低缺陷石墨烯的质量之比不低于1.1:1，例如为1.1-2.1:1。
为了提高薄膜成型中低缺陷石墨烯的分散稳定(浸润)，所述分散剂包括薄膜分散剂。在一些典型的实施方式中，所述的薄膜分散剂为C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基磺酸盐、烷基多聚葡萄糖、环氧丙烷、脂肪醇烷氧基化物、羟丙基甲基纤维素和聚乙烯吡咯烷酮中的一种或任意组合。由于带有大量极性官能团的薄膜分散剂在碳化过程中会放出气体，存在对电红外致热膜的完整性和致密性造成破坏的可能，在一些典型的实施方式中，所述薄膜分散剂在制膜浆料中质量占比不超过的1％。碳化后薄膜分散剂质量占比相比成膜剂碳化后的质量占比可忽略不计。所述列举的有机聚合物均为市售常规的分散剂。
在一些典型的实施方式中，所述C12-C16烷基二苯基醚单磺酸盐例如为十六烷基二苯基醚单磺酸钠。所述C12-C16烷基二苯基醚二磺酸盐例如为十六烷基二苯基醚二磺酸钠。所述对C12-C16烷基苯磺酸酯例如为对甲基苯磺酸丙酯。所述C12-C16烷基磺酸盐例如为十六烷基磺酸钠。
为进一步优化导电层的可加工性性能，所述浆料还包括添加剂；所述添加剂为流平剂、增稠剂、触变剂、导电剂中的任意一种或多种组合。所述添加剂的添加量与低缺陷石墨烯的质量比不大于1:20。
在一些实施方式中，所述制膜浆料的粘度>3000Pa·s，固含量>10wt％。在一些实施方式中，所述制膜浆料的固含量为18.9-25.5％，例如19％、20％、21％、22％、23％、24％、25％，粘度为3800-7300Pa·s，例如4000-7300Pa·s、3800-7000Pa·s或4500-6500Pa·s，诸如4000Pa·s、4500Pa·s、5000Pa·s、5500Pa·s、6000Pa·s、6500Pa·s、7000Pa·s、7200Pa·s。
在一些实施方式中，所述制膜浆料中的低缺陷石墨烯的D50粒度为10-20μm。
在一些实施方式中，所述制膜浆料的制备方法包括以下步骤：将主要由低缺陷石墨烯粉料、无机填充剂、浆料分散剂和部分溶剂组成混合料进行砂磨后加入成膜剂、薄膜分散剂和剩余溶剂，混匀得到的。通过砂磨处理，可以使低缺陷石墨烯获得较好的分散，避免片层回叠。尤其是采用的低缺陷石墨烯中缺乏缺陷和氧化官能团，与溶剂的极化作用较差，对低缺陷石墨烯原料进行破碎、对混合料进行砂磨处理以及使用分散剂均能够促进低缺陷石墨烯在浆料中的均匀分散并且避免片层回叠，保证低缺陷石墨烯以少片层且结构完整的形式呈现在电红外致热膜中，从而进一步提高膜的红外辐射性能。
为降低成本并提高分散效果，在一些实施方式中，所述溶剂为甲醇、乙醇、正丁醇、丙二醇、乙酸乙酯、甲苯、二甲苯、N-甲基吡咯烷酮(NMP)、丙酮、N,N-二甲基甲酰胺、四氢呋喃、环氧活性稀释剂、1,4-丁二醇二缩水甘油醚中的一种或任意组合。
为平衡砂磨分散效果，在一些典型的实施方式中，低缺陷石墨烯中溶剂与浆料分散剂的质量比为8～15:1～5诸如10～15:1～5、11～15:1～4或12～15:1～3，例如为2.9～9.5:1。制备低缺陷石墨烯浆液时采用部分溶剂作为主溶剂，在制得的低缺陷石墨烯浆液中加入的剩余溶剂作为稀释溶剂。在一些典型的实施方式中，所述主溶剂选自N-甲基吡咯烷酮、乙酸乙酯中的一种或任意组合；所述稀释溶剂为N-甲基吡咯烷酮。稀释溶剂与主溶剂的质量比为39～54.8:11.4～22.1，例如40～54:11.5～22.0、39～54:12～20或40～52:15～20。
在一些实施方式中，所述碳化处理的温度为600～1200℃，时间不少于4h。在一些实施方式中，碳化处理前，先升温至400℃保温1h，然后再升温至碳化处理的温度进行碳化处理。所述升温的速率为5℃/min。碳化处理后先由碳化处理的温度降温至500℃保温1h，再进行降温。所述碳化处理在保护性气氛中进行。
本公开一实施方式提供一种电红外致热装置，该装置包括：
电红外加热元件；
上述任意一种电红外致热膜，设置于所述电红外加热元件的内壁上，并被密封于所述电红外加热元件内部。
在一些实施方式中，电红外加热元件包括灯式电红外加热元件、管式电红外加热元件或板式电红外加热元件的一种。
在一些实施方式中，电红外加热元件可以为管式电红外加热元件。在一些实施方式中，管式电红外加热元件包括管体。
在一些实施方式中，电红外致热装置包括：
管式电红外加热元件和上述任意一种的电红外致热膜；
管式电红外加热元件包括管体和电极；电红外致热膜设置于管体的内壁上，电极与电红外致热装置电连接，并在通电时使电红外致热膜发热。
本公开一实施方式提供一种电红外致热装置，该装置所采用的技术方案为：
一种电红外致热装置，包括：管体；上述任意一种的电红外致热膜，设置于所述管体的内壁上，并被密封于所述管体内部；两个电极，均与所述电红外致热装置电连接，并在通电时使电红外致热膜发热。
本公开的电红外致热装置，采用上述具有较低膨胀率的电红外致热膜，使得电红外致热膜与基体在通电情况下具有较高的膨胀率匹配程度，避免电红外致热膜从基体上脱落，从而具有较长的使用寿命。
本公开的电红外致热装置，将本公开的电红外致热膜设置于管体(或电红外加热元件)内壁从而实现快速升温至高温(＞300℃)，并且电红外致热膜以低缺陷石墨烯、无机填充剂和无定型碳为主要成分，可以确保电红外致热装置在反复升降温及高温工况下工作的性能与结构稳定性。由于电红外致热膜充分保留了低缺陷石墨烯的片层结构特征，可以使电红外致热装置充分发挥低缺陷石墨烯材料高红外辐射率和高导热的本征优点。
为了进一步延长电红外致热膜的使用寿命，管体(或电红外加热元件)内部被抽真空或充入惰性气体。将管状(或电红外加热元件)的基体内部抽真空或在管状的基体内充入惰性气体，可以避免低缺陷石墨烯和无定型碳在高温下氧化。
在一些实施方式中，管体为石英管、陶瓷管、玻璃管中的一种，例如石英管。在一些实施方式中，选择石英管作为管体，本公开的电红外致热膜与石英之间膨胀系数相差较小，以石英管为基体能够进一步延长电红外致热装置的使用寿命。
在一些实施方式中，所述管体的内径为8～13mm诸如8mm、8.5mm、9mm、9.5mm、10mm、10.5mm、11mm、12mm、13mm。所述管体的壁厚为0.1～2mm诸如0.2mm、0.5mm、0.7mm、1mm、1.5mm、1.8mm、2mm。
在一些实施方式中，电红外加热元件可以为板式电红外加热元件。在一些实施方式中，板式电红外加热元件包括陶瓷板式电红外加热元件、云母板式电红外加热元件、石英板式电红外加热元件以及带陶瓷镀层的金属板式电红外加热元件。
在一些实施方式中，电红外致热装置包括：
板式电红外加热元件和上述任意一种的电红外致热膜；
板式电红外加热元件包括板体和电极；电红外致热膜设置于板体的内壁上，电极与电红外致热装置电连接，并在通电时使电红外致热膜发热。在一些实施方式中，板体包括第一基板和第二基板。在一些实施方式中，第一基板和第二基板通过诸如热压等形式贴合以形成密封体；电红外致热膜位于第一基板和第二基板贴合侧的第一基板上、或者第二基板上或者第一基板和第二基板两者上。在一些实施方式中，板体的材质包括石英、高硼硅、云母、具有绝缘陶瓷层的碳钢板、具有绝缘陶瓷层的铝合金板。
本公开的电红外致热装置在制备时，包括以下步骤：将主要由低缺陷石墨烯、无机填充剂、成膜剂和溶剂组成的浆料涂覆在管体的内壁上成膜，挥发溶剂后进行碳化处理，降温，然后安装电极并对管体进行密封。
本公开采用的低缺陷石墨烯既可以购买获取，也可以按照申请公布号为CN108622887A的中国公开专利申请公开的方法进行制备。
以下结合具体实施方式本公开的技术方案作进一步的说明。
实施例
一、本公开的电红外致热膜的实施例
实施例1
本实施例的电红外致热膜，由以下重量份数的组分组成：无定型碳5份、低缺陷石墨烯10份、无机填充剂10份；其中，无机填充剂为纳米二氧化硅，D50粒度为20nm；低缺陷石墨烯的D50粒度为15μm，低缺陷石墨的拉曼光谱图具有2D峰，且2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少5cm -1以上(包括5cm -1)，且D峰强度与G峰强度之比为1/20，同时低缺陷石墨烯的碳氧摩尔比为30:1；电红外致热膜的厚度为15μm。
实施例2-6
实施例2-6中的电红外致热膜均由无定型碳、低缺陷石墨烯和无机填充剂组成；各实施例中的低缺陷石墨烯的拉曼光谱图具有2D峰，且2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少5cm -1以上(包括5cm -1)，且D峰强度与G峰强度之比为1/20，同时低缺陷石墨烯的碳氧摩尔比为30:1；各实施中电红外致热膜中无定型碳、低缺陷石墨烯和无机填充剂的重量份数以及低缺陷石墨烯的粒度、无机填充剂的种类和D50粒度、电红外致热膜的厚度见表1。
表1.实施例1～6中各组分种类、规格和含量
Figure PCTCN2022071866-appb-000001
实施例7～12中采用的低缺陷石墨烯原料购自郑州新材科技有限公司(CP 1002低缺陷石墨烯精细粉体系列产品)，为物理膨爆法制备的石墨烯。对该低缺陷石墨烯原料进行拉曼光谱检测，低缺陷石墨烯的拉曼光谱图具有2D峰，且2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少5cm -1以上(包括5cm -1)，且D峰强度与G峰强度之比为1/20，碳氧摩尔比为30:1。
二、本公开的电红外致热膜的制备方法的实施例
实施例7
本实施例的电红外致热膜的制备方法，以实施例1的电红外致热膜的制备方法(组分配比、规格和参数)为例，包括以下步骤：
1)将低缺陷石墨烯原料通过气流破碎处理，得到低缺陷石墨烯粉料；
2)制备制膜浆料：
将浆料分散剂和主溶剂混合均匀得到复合基液，然后向复合基液中加入主碳材和无机填充剂，继续搅拌至主碳材和无机填充剂在复合基液中分散均匀，再在20℃下以0.3mm的锆球为研磨介质，在15m/s的线速度下砂磨，得到低缺陷石墨烯分散液；然后向低缺陷石墨烯分散液加入成膜剂、稀释溶剂和薄膜分散剂，然后在40℃下以500rpm的速度搅拌2h，得到制膜浆料；
所采用的浆料分散剂为环氧乙烷和二元酸酯(DBE)的组合，环氧乙烷和DBE的质量比为1:2，主溶剂为N-甲基吡咯烷酮(NMP)，无机填充剂为纳米二氧化硅，成膜剂为聚丙烯腈(PAN)，稀释溶剂为N-甲基吡咯烷酮，薄膜分散剂为聚乙烯吡咯烷酮(PVP K30)；
所采用的主碳材为低缺陷石墨烯，低缺陷石墨烯分散液中，低缺陷石墨烯的粒度D50为15μm，无机填充剂的粒度D50为20nm；
采用的浆料分散剂占制膜浆料质量的15％，采用的主溶剂占制膜浆料质量的44.1％，采用的低缺陷石墨烯粉料和无机填充剂均占制膜浆料质量的7.4％，采用的成膜剂占制膜浆料质量的3.7％，采用的薄膜分散剂占制膜浆料质量的0.7％，采用的稀释溶剂占制膜浆料质量的29.1％；得到的制膜浆料的固含量为19.1wt％、粘度为6000Pa·s。
3)将制膜浆料灌入内径为8mm的石英管中，再在50℃下将浆料在石英管内反复颠倒，最后将浆料从石英管两端倒出，直到从两端分别倒出浆料时，两端在1min内无浆液流出；
4)将步骤3)中倒出浆料的石英管置于90℃鼓风烘箱中，然后将石英管以4转/分钟的速度沿同一方向同轴旋转30min直至管内壁浆料定型；
5)固化后的石英管放入200℃鼓风烘箱干燥30min，得厚度为20μm均匀管内壁涂层；
6)在0.25L/min流速的氩气管式炉中进行升温，升温速率5℃/min，在400℃保温1h后升温至800℃，保温4h，再降温至500℃保温1h后自由降温，即在石英管内壁形成厚度为15μm的电红外致热膜。
实施例8-12
实施例8-12分别对应实施例2-6的电红外致热膜的制备方法(组分配比、规格和参数)，实施例8-12的电红外致热膜的制备方法参照实施例7的电红外致热膜的制备方法，各实施例中制得的制膜浆料组成见表2和表3，制得的制膜浆料的固含量和粘度、采用的管体以及管体的内径和壁厚、制得电红外致热膜的厚度见表4，表2-4中未述及之处均与实施例7的电红外致热膜的制备方法相同。
表2实施例8-9的电红外致热膜的制备方法中制膜浆料的组成
Figure PCTCN2022071866-appb-000002
表3实施例10-12的电红外致热膜的制备方法中制膜浆料的组成
Figure PCTCN2022071866-appb-000003
表4实施例8-12的电红外致热膜的制备方法中制膜浆料的固含量和粘度、采用的管体以及管体的内径和壁厚、制得电红外致热膜的厚度
Figure PCTCN2022071866-appb-000004
本公开的电红外致热膜的制备方法的其他实施例，还可以将实施例9和实施例12的电红外致热膜的制备方法中的石英管替换为陶瓷管，将实施例11的制备方法中的石英管替换为玻璃管。
三、本公开的电红外致热装置的实施例
实施例13
实施例13的电红外致热装置如图1-图2所示，包括石英管1、电红外致热膜2、两个引出电极3、两个密封头4；其中电红外致热膜2采用由实施例7的制备方法制备获得的电红外致热膜涂覆于石英管1的内壁上，两个引出电极3分别在石英管1的两端嵌套于石英管1内并分别在石英管1的两端与电红外致热膜2电连接；两个密封头4分别位于石英管1的两端并对石英管1形成密封，两个引出的电极3以及电红外致热膜2位于石英管1的密封空间内，两个密封头4上分别设有穿线孔，用于供与对应端的引出电极电连接的导线穿过。
实施例14
本实施例的电红外致热装置与实施例13的电红外致热装置的区别仅在于：石英管内壁的电红外致热膜是由实施例8的制备方法制得的电红外致热膜。
实施例15
本实施例的电红外致热装置与实施例13的电红外致热装置的区别仅在于：石英管内壁的电红外致热膜是由实施例9的制备方法制得的电红外致热膜。
实施例16
本实施例的电红外致热装置与实施例13的电红外致热装置的区别仅在于：石英管内壁的电红外致热膜是由实施例10的制备方法制得的电红外致热膜。
实施例17
本实施例的电红外致热装置与实施例13的电红外致热装置的区别仅在于：石英管内壁的电红外致热膜是由实施例11的制备方法制得的电红外致热膜。
实施例18
本实施例的电红外致热装置与实施例13的电红外致热装置的区别仅在于：石英管内壁的电红外致热膜是由实施例12的制备方法制得的电红外致热膜。
实施例13～18的电红外致热装置在制备时，分别按照所采用的电红外致热膜的制备方法，在石英管内形成电红外致热膜后，将引线焊接在引出电极上，然后石英管两端的电红外致热膜上涂敷纳米银胶，然后将两引出电极分别从石英管两端置于石英管内，并在电红外致热膜涂覆纳米银胶的位置与电红外致热膜贴合固定，然后在高纯氩气环境中分别在石英管两端安装密封头，并将引线通过对应端的密封头上预留的穿线孔引出后，采用耐温密封胶对引线与穿线孔之间、以及密封头与石英管之间的间隙进行密封。
实施例19
本实施例的电红外致热装置，仅是将实施例13的电红外装置中的石英管替换为陶瓷管，并且高温玻璃管只有一端的密封头上开设穿线孔，穿线孔的数量为两个，用于供与两个引出电极电连接的导线分别穿过。
实施例20
本实施例的电红外热装置，仅是将实施例18的电红外致热装置中的密石英管替换为高温玻璃管且封头替换为热塑封，此处不再赘述。
实施例21
本实施例的电红外致热装置如图4所示，包括板体5、电红外致热膜2、凹字形金属电极6；其中，板体5包括第一基板51和第二基板52，第一基板51和第二基板52材质结构相同，均为石英材质。电红外致热膜2采用实施例7步骤1)至2)的制备方法制备得到的制膜浆料涂覆于第二基板52的表面，并且在50℃下静置固定，直至将第二基板52垂直时，其上的浆料在1min内无浆液流出，随后将涂覆有电红外致热膜2的第二基板52置于90℃鼓风烘箱中30min直至该第二基板52壁上浆料定型，并按照实施例7步骤5)至6)操作，在该第二基板52上形成厚度为25μm的电红外致热膜。
将两个凹字形金属电极6分别固定在电红外致热膜2的两端，与电红外致热膜2连接并密封嵌套于第一基板51和第二基板52之间，凹字形金属电极6的两臂作为电极露出板外用于接线。再将第一基板51覆盖在涂覆有电红外致热膜2的第二基板52的表面，通过热压封装的方式紧密贴合，形成紧密贴合的密封空间(选用凹字形金属电极6以减少压封应力和漏气点)。
实施例22
本实施例的电红外致热装置与实施例21相同。不同之处为板体5为高硼硅材质，通过热压进行封装。
实施例23
本实施例的电红外致热装置与实施例21相同。不同之处为板体5为云母材质，通过耐高温粘合剂进行封装。
实施例24
本实施例的电红外致热装置与实施例21相同。不同之处为板体5为绝缘陶瓷层的碳钢板材质且绝缘层在内，碳钢材质向外。通过耐高温粘合剂进行封装。
实施例25
本实施例的电红外致热装置与实施例21相同。不同之处为板体5为绝缘陶瓷层的铝合金板材质且绝缘层在内，铝合金材质向外。通过耐高温粘合剂进行封装。
对比例中采用的氧化还原石墨烯为HUMMER法制备的氧化还原石墨烯，具有大量的缺陷。
对比例1-6
对比例1-6的电红外致热装置，与实施例13的电红外致热装置的区别仅在于石英管上的电红外致热膜。
对比例1-6的石英管内壁上的电红外致热膜在制备时参照实施例7的电红外致热膜的制备方法。对比例2-6中，为保证在石英管内部能够涂覆均匀形成15μm厚的电红外致热膜，调整稀释溶剂的加入比例(固含量)，另外各对比例制得的制膜浆料中的主碳材及固含量、砂磨线速度及循环次数、制得的电红外致热膜的厚度以及电红外致热膜中主碳材、填充剂和无定型碳的质量比见表5，未述及内容完全同实施例7。
表5对比例1-6的电红外致热装置的石英管内壁的电红外致热膜的组成、厚度以及制备方法
Figure PCTCN2022071866-appb-000005
Figure PCTCN2022071866-appb-000006
实验例1
比较实施例13、16、18和对比例1～6中在石英管上形成电红外致热膜的过程中制膜浆料的成膜性能，结果如表6所示。
表6实施例13、16、18和对比例1～6中制膜浆料的成膜特性
Figure PCTCN2022071866-appb-000007
由表6可知，本公开的电红外致热膜(实施例13、16、18为例)采用的是低缺陷的石墨烯，其溶剂化性能低，通过机械共混可实现提高低缺陷石墨烯在电热膜材料中的固含占比。
对比例中采用的市面上的氧化还原石墨烯的缺陷浓度较高、氧化还原法制备出的石墨烯片径一般情况下较小，在浆料内溶剂化程度较高，在石墨烯分散液的组分及各组分含量一致的情况下，采用市面上氧化还原石墨烯的浆料其稠度显著上升，流动性显著下降，无法采用步骤4)(实施例7的步骤4)中提及的方法或其他方式实现在管内的均匀涂覆。在选用高片径石墨烯材料后，由于氧化还原石墨烯边缘态浓度(密度)下降，溶剂化程度降低，修复后的氧化石墨烯材料由于(110)面上缺陷降低，可进一步降低溶剂化程度，因此可显著提高浆料固含量。同理，由于碳纳米管和纳米碳微球比表面积较大，溶剂化程度高，同样无法提高固含量。因此在对比例2-6中采用降低固含量的做法进行浆料制备。然而盲目降低浆料固含量以提高浆料流动性的做法既降低了浆料的粘度(不是稠度)不利于浆料在光滑管壁内的稳定附着(对比例2)，并且容易使涂覆浆料在烘干过程中由于大量溶剂蒸发造成干膜内部结构上的疏松出现针孔等现象，不利于干燥后材料的成膜性。
实验例2～4中，所有平行对比测试在开放、无对流环境中进行，若无特别指出，所有测试环境温度为25±0.5℃。实施例13、16、18以及对比例4～6电红外致热装置的外径为 10mm，有效发热长度为285mm，即有效发热面积为89.5cm 2。测温采用红外成像仪，精度为±0.1℃，误差±2℃。实验用电源为稳压可调交流电源，频率50Hz，精度±0.1V，误差±1V。
实验例2
在定功率下180W下对实施例13、16、18和对比例4～6的电红外致热装置进行反复升温测试，恒温后保温时间15分钟，待冷却至26℃以下后再次测试，升温至恒温温度进行保温的次数为10次，各电红外致热装置的有效加热面积、恒温温度、升温至恒温温度的时间和反复升温后电红外致热装置的状态，见表7；测试所得各电红外致热装置的升温曲线见图3。
表7定功率下电红外致热装置的表面温度与耐久性
Figure PCTCN2022071866-appb-000008
由表7的数据可知，本公开实施例制备的电红外致热膜(实施例13、16、18为例)具有较高的表面温度和优异的耐久性，同时以本公开实施例所包含的低缺陷石墨烯在电热膜材料中的高固含占比，体现了本公开的电红外致热膜在反复升温测试中的高耐久性。在加热材料中导电回路由主碳材-主碳材以及主碳材-非定型碳通过物理接触实现导电，由本公开实施例制备的电红外致热膜(实施例13、16、18为例)完全满足了在此过程中需要应对的特性：(a)升降温过程中薄膜的整体应力变化；(b)反复升降温过程中主碳材膨胀收缩后导电回路的接触稳定性：点-点接触<线-线接触<面-面接触；(c)高温与电场环境下主碳材与氧化物陶瓷的化学稳定性。
对比例4中采用的商用石墨烯，其由于缺陷高、热稳定性差，即便在高纯惰性气体的保护下，高温通电的工况依然会导致其发生结构重排，导致氧化还原石墨烯材料发生不可逆转的结构损伤，造成其电阻不断升高，影响其使用寿命。对比例4中所采用的石墨烯虽然通过高温法去除了绝大多数第三类缺陷，但是第一类缺陷是难以通过该工艺进行修补的。因此其不满足上述(c)要求。对比例5中碳纳米管虽然结构稳定性较好，对电红外致热膜具有结构稳定的效果，但是由于其结构原因，导致其分散性能差、难以提高固含占比外导致难以降低溶剂含量对成膜的影响。此外，其一维的导电导热特性令碳纳米管成膜后沿壁径的导热能力相对较低。对比例6中Super-P作为纳米碳球虽然具有良好的三维导电导热效果，由于与其它材料采用点接触，且自身在加热过程中较容易受到布朗运动以及热膨胀应力的影响，使其构建的三维导电网络局部遭到破坏，不利于工况下维持电红外致热膜的整体电热性能。对比例6中采用的super-P为纳米碳微球，难以满足(b)要求。因此在多次升降温后主碳材与主碳材接触由于热胀冷缩发生短路导致局部温度过高和放电进而导致薄膜开裂。
实验例3
分别对比本公开的实施例13、16、18和市售的几种发热管的升温速率，结果见表8。
可采购到的作为高温空气热源(额定功率≥400W，工作温度≥300℃，可空烧)的市售加热管全部为采用发热丝沿管体中轴穿过的组装方式，市售消毒柜发热管的额定功率400W(加热体为螺旋状合金加热丝)，市售光波炉发热管的额定功率400W(加热体为拉直碳纤维加热丝)，市售碳纤维发热管的额定功率800W(加热体为拉直碳纤维)，市售金属丝短波红外发热管的额定功率500W(加热体为拉直合金加热丝)。采用定功率对加热管进行升温，温度采样间隔为7.5Hz，测试管体表面升温至300℃消耗时间，并计算功率密度，结果如表8所示。
表8实施例和对比例在开放环境中加热管表面升温速度测试测试结果
Figure PCTCN2022071866-appb-000009
由表8的数据可知，实施例的电红外致热装置与对比例的发热管相比，在同等功率或更低功率/功率密度下，开放环境下实施例的电红外致热装置的管体表面升温速度具有显著的优势。本公开的电红外致热装置相比市售的各类加热管在电能利用率、传热和加热效率上有显著的提高。以市售的金属丝短波红外发热管为例，其加热体体积最小，外轮廓距离管体距离最远，升温速度最慢，体现本公开的电红外致热装置带来的升温性能优势。
实验例4
在定功率下(180-185W)通过红外成像测温仪(FLIR E60，误差：±2℃)对实施例13、16、18以及实验例3中列举的几种市售发热管进行工况温度测试，并根据史提芬-玻尔兹曼定律计算其红外辐射转化率的计算，相应的测试参数与结果如表9所示。
表9定功率下加热管表面温度与对应红外辐射转化率
Figure PCTCN2022071866-appb-000010
由表9的数据可知，实施例的电红外致热装置，其红外转化率达到75％以上，且发热体紧贴加热装置外壁，因此判断其换热机制为：以辐射换热为主，以导热方式为辅。相比一般市售加热管其发热体与管壁分离的设计，装置外壁温度直接来自加热膜，不再存在对流换热和发热体－内环境－管壁的传热机制。具有较低的管表-加热体温度差，电热能利用率更高，因此在红外辐射转化率上具有显著的优势。相较于市售电热管普遍40-56.2％的电红外转化率，实施例的电红外致热装置的电红外转化率在市售加热管平均功率(400-500W)不足一半的情况下仍然具有>75％的红外辐射转化率，这是由于其优越的红外辐射性能很大程度上是由于低缺陷石墨烯的额外红外辐射能力与电红外致热膜在高温下所具备的优越材料力学性能从而实现与管壁的无缝传热设计带来的。
需要说明的是上述实验例中的是实施例13、16和18仅作为与对比例进行比较的示例性的说明，并不能限制本公开说明书和权利要求的范围，同时需要说明本公开实施例14、15、17、19-20以及其他实施方式制备得到的电红外热装置同样具有与实施例13、16和18在涉及上述实验例的所有实验效果上具有相近的技术效果。
由于本公开的电红外致热装置的管体内壁与电红外致热膜在升温过程中膨胀系数低，降低了电红外致热膜与装置内壁发生分离的几率，从而保证电红外致热装置结构与性能的稳定性。
工业实用性
本公开提供的电红外致热膜中，低缺陷石墨烯、无机填充剂、无定型碳能够降低电红外致热膜的体积膨胀系数，缩小电红外致热膜与陶瓷、石英、高硼耐温玻璃等基体材料的体积膨胀系数的差距，避免电红外致热膜从这些材料表面脱落，延长采用电红外致热装置的使用寿命，由本公开方法制备的电红外致热膜以及包括其的电红外制热装置具有优异的应用价值。

Claims (16)

  1. 一种电红外致热膜，其特征在于：主要由以下重量份数的组分组成：低缺陷石墨烯10～15份、无机填充剂5～20份和无定型碳5～10份。
  2. 根据权利要求1所述的电红外致热膜，其特征在于：所述低缺陷石墨烯的拉曼光谱图中，D峰强度与G峰强度之比不大于1/10，且低缺陷石墨烯中碳氧摩尔比不小于20:1。
  3. 根据权利要求1或2所述的电红外致热膜，其特征在于：所述低缺陷石墨烯的拉曼光谱图中具有2D峰，且所述2D峰与G峰的间距与天然鳞片石墨的2D峰与G峰的间距相比，减少≥5cm -1。
  4. 根据权利要求1-3任一所述的电红外致热膜，其特征在于：所述无机填充剂在电红外制热膜的工况温度区间或在0-600℃范围内的热膨胀系数≤5×10 -7/K。
  5. 根据权利要求1-4任一所述的电红外致热膜，其特征在于：所述无机填充剂的D50粒度小于所述低缺陷石墨烯的D50粒度；
    优选地，所述无机填充剂粒度D50小于所述低缺陷石墨烯D50粒度的1/150。
  6. 根据权利要求1-5任一所述的电红外致热膜，其特征在于：所述无机填充剂为氧化铝陶瓷粉、氧化锆陶瓷粉、氧化硅粉体、云母粉、碳化硅粉填料中的任意一种或任意组合；所述无机填充剂的D50粒度≤100nm。
  7. 根据权利要求1-6任一所述的电红外致热膜，其特征在于：所述电红外致热膜的厚度不大于100μm。
  8. 根据权利要求1-6任一所述的电红外致热膜，其特征在于：所述电红外致热膜的厚度为10～30μm。
  9. 一种如权利要求1所述的电红外致热膜的制备方法，其特征在于：包括以下步骤：
    将主要由低缺陷石墨烯、无机填充剂、成膜剂和溶剂组成的浆料涂覆成膜，挥发溶剂后进行碳化处理，即得；所述成膜剂为有机聚合物。
  10. 根据权利要求9所述的电红外致热膜的制备方法，其特征在于：所述有机聚合物为聚烯烃、聚苯乙烯、聚丙烯酸酯类聚合物、聚氧化乙烯、聚偏氟乙烯、聚酰亚胺、聚氨酯、聚丙烯腈、酚醛树脂中的一种或任意组合。
  11. 根据权利要求9或10所述的电红外致热膜的制备方法，其特征在于：所述浆料还包括石墨烯分散剂；所述石墨烯分散剂包括浆料分散剂和薄膜分散剂；所述浆料分散剂选自二苯醚、C12-C16烷基苯磺酸酯、环氧乙烷、聚乙二醇、二元酸酯、C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基二苯基醚二磺酸盐、C12-C16烷基磺酸盐、对C12-C16烷基苯磺酸酯中的一种或任意组合；所述薄膜分散剂选自C12-C16烷基二苯基醚单磺酸盐、C12-C16烷基磺酸盐、烷基多聚葡萄糖、环氧丙烷、脂肪醇烷氧基化物、羟丙基甲基纤维素、聚乙烯吡咯烷酮中的一种或任意组合。
  12. 根据权利要求9-11中任意一项所述的电红外致热膜的制备方法，其特征在于：所述碳化处理的温度为600～1200℃，时间不少于4h。
  13. 一种电红外致热装置，其特征在于：包括：
    电红外加热元件；
    如权利要求1～8中任意一项所述的电红外致热膜，设置于所述电红外加热元件的内壁上，并被密封于所述电红外加热元件内部；
    优选地，所述电红外加热元件包括灯式电红外加热元件、管式电红外加热元件或板式电红外加热元件的一种。
  14. 一种电红外致热装置，其特征在于：包括：
    管体；
    如权利要求1～8中任意一项所述的电红外致热膜，设置于所述管体的内壁上，并被密封于所述管体内部；
    两个电极，均与所述电红外致热装置电连接，并在通电时使电红外致热膜发热。
  15. 根据权利要求14所述的电红外致热装置，其特征在于：所述的管体为石英管、陶瓷管或玻璃管。
  16. 一种电红外致热装置，其特征在于，包括：
    板式电红外加热元件；
    如权利要求1～8中任意一项所述的电红外致热膜；
    所述板式电红外加热元件包括板体和电极；所述电红外致热膜设置于所述板体的内壁上，并被密封于所述板体内部；所述电极与所述电红外致热装置电连接，并在通电时使所述电红外致热膜发热。
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