CN115141001A - Graphite-based electric heating material, preparation method thereof and electric heating equipment - Google Patents
Graphite-based electric heating material, preparation method thereof and electric heating equipment Download PDFInfo
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- CN115141001A CN115141001A CN202210426502.5A CN202210426502A CN115141001A CN 115141001 A CN115141001 A CN 115141001A CN 202210426502 A CN202210426502 A CN 202210426502A CN 115141001 A CN115141001 A CN 115141001A
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
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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
- H05B3/02—Details
- H05B3/06—Heater elements structurally combined with coupling elements or holders
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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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater 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—Heater 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
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/90—Electrical properties
- C04B2111/94—Electrically conducting materials
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- 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
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The invention provides a graphite-based electric heating material, a preparation method thereof and electric heating equipment. The graphite-based electric heating material comprises mixed graphene, vermicular graphite and carbon fiber, and at least part of the graphene is inserted into the vermicular graphite. The preparation method of the graphite-based electric heating material comprises the following steps: step S1, mixing graphene and vermicular graphite to enable part of graphene to be inserted into the vermicular graphite to obtain a compound; and S2, mixing the carbon fiber product with the composite to obtain the graphite-based electric heating material. The graphite-based electric heating material provided by the application is inserted into the vermicular graphite through at least partial graphene and cooperates with the carbon fibers as a framework, so that the cost is low, the excellent heat dissipation performance is realized, the flexibility is good, the repeated bending resistance can be realized, the aging resistance is excellent, and the wide application prospect is realized.
Description
Technical Field
The invention relates to the technical field of electric heating materials, in particular to a graphite-based electric heating material, a preparation method thereof and electric heating equipment.
Background
The traditional heating modes in the north mainly comprise coal, natural gas, wood and the like, and the heating modes can discharge a large amount of carbon dioxide and smoke, so that potential safety hazards exist in the using process, and air pollution can be caused. The situation can be effectively relieved by adopting central heating, but the central heating equipment is complex and has poor flexibility. Therefore, oil tincture heaters, electric heating equipment such as 'little sun' and the like appear in the market, and the electric heating equipment can be used for heating flexibly.
The existing electric heating equipment mainly adopts metal electric heating materials, organic electric heating materials or inorganic electric heating materials as heat dissipation materials. The metal electric heating material has complex processing technology and higher cost, and cannot be applied on a large scale. The organic electric heating material is prepared by adding conductive particles into organic macromolecules to prepare a film or is coated on the surface of an insulator, has good flexibility, is easy to age and cannot be used for a long time. The inorganic material electric heating material is a conductive film prepared by adding a flame retardant into an inorganic conductive material, but the inorganic material electric heating material has poor flexibility, large brittleness and limited application range.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention mainly aims to provide a graphite-based electric heating material, a preparation method thereof and electric heating equipment, and aims to solve the problem that a heat dissipation material of electric heating equipment in the prior art cannot have flexibility and aging resistance at low cost.
In order to achieve the above object, according to one aspect of the present invention, there is provided a graphite-based electrocaloric material including mixed graphene, vermicular graphite, and carbon fibers, with at least part of the graphene intercalated into the vermicular graphite.
Furthermore, the graphite-based electrothermal material is a graphite-based electrothermal film, and the density of the graphite-based electrothermal film is 1.5-2.0g/cm 3 The thickness is 40 μm-2mm.
Further, the mass ratio of the vermicular graphite to graphene is 100.5-8, preferably 100.
Further, the mass ratio of the total mass of graphene and vermicular graphite to carbon fiber is 100, 0.0034-1, preferably 100, 0.0068-0.8.
Further, the graphene electrothermal film comprises a plurality of layered units, each layered unit comprises graphene and vermicular graphite, the layered units and the carbon fibers are alternately stacked, and at least part of the carbon fibers are embedded in the layered units.
According to another aspect of the present invention, there is also provided a method for preparing any one of the graphite-based electric heating materials provided above, the method comprising: step S1, mixing graphene and vermicular graphite to enable at least part of graphene to be inserted into the vermicular graphite to obtain a compound; and S2, mixing the carbon fiber product with the compound to obtain the graphite-based electric heating material, wherein the carbon fiber product is made of carbon fibers.
Further, the step S1 includes: step S11, mixing the graphene solution and the vermicular graphite to enable at least part of graphene to be inserted into the vermicular graphite to obtain a composite system; and S12, drying the composite system agent to obtain a composite.
Further, in the step S11, the mass concentration of the graphene solution is 0.1 to 8%, preferably 0.5 to 5%.
Further, the above mixing means includes at least one of stirring, kneading and ultrasonication.
Further, the vermicular graphite is obtained by treating expandable graphite at 500-950 ℃ for 5-60 s.
Further, the step S12 also includes a process of rolling the composite sheet to form the composite sheet, and the density of the composite sheet is preferably 0.064-0.44g/cm 3 。
Further, the step S2 includes: alternately laminating and pressing the carbon fiber products and the compound to obtain the graphite-based electric heating material; the carbon fiber product is made of carbon fibers.
Furthermore, the carbon fiber product is carbon fiber wires or carbon fiber cloth, the diameter of the carbon fiber wires is preferably 6-8 μm, and the density of the carbon fiber cloth is preferably 4mm multiplied by 4mm-10mm multiplied by 10mm.
According to a third aspect of the present invention, there is provided an electrothermal apparatus comprising a heat sink material, the heat sink material being any one of the graphite-based electrothermal materials provided above or the graphite-based electrothermal material obtained by any one of the preparation methods provided above.
Further, the electric heating equipment also comprises a current collector which is electrically connected with the graphite-based electric heating material.
Further, the current collector is arranged on at least one edge of the graphite-based electric heating material, and preferably, the current collector and the graphite-based electric heating material are coated by a plastic package film.
Furthermore, the electric heating equipment further comprises a temperature controller, a fuse, a switch and a power supply, wherein the current collector is electrically connected with the power supply, and the temperature controller, the fuse and the switch are arranged on a circuit between the current collector and the power supply.
The graphite-based electric heating material provided by the application is inserted into the vermicular graphite through at least partial graphene and cooperates with the carbon fibers as a framework, so that the cost is low, the excellent heat dissipation performance is realized, the flexibility is good, the repeated bending resistance can be realized, the aging resistance is excellent, and the wide application prospect is realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a photograph showing composite sheets and carbon fiber sheets alternately arranged in a stacked state in step (4) according to example 1 of the present invention;
FIG. 2 shows an SEM image of a composite obtained in step (2) of example 1;
FIG. 3 is a fracture plane view of a graphite-based electrothermal film provided in example 1;
fig. 4 shows a schematic structural diagram of an electric heating device provided by the embodiment 27.
Wherein the above figure 4 includes the following reference numerals:
1. product hooking; 2. screw fixing holes; 3. a thermocouple; 4. a zero line binding post; 5. thermocouple terminals; 6. a live wire terminal; 7. a ground wire terminal; 8. a heat dissipation area; 9. a graphene electrothermal film; 10. a current collector; 11. a polytetrafluoroethylene film; 12. a protection plate; 13. a switch; 14. a fuse; 15. a temperature controller.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the application, the heat dissipation material adopted by the existing electric heating equipment has the problem that the heat dissipation material cannot have flexibility and aging resistance at low cost, and in order to solve the technical problem, the application provides a graphite-based electric heating material, a preparation method thereof and electric heating equipment.
In an exemplary embodiment of the present application, there is provided a graphite-based electrocaloric material comprising mixed graphene, vermicular graphite and carbon fibers, with at least a portion of the graphene intercalated into the vermicular graphite.
According to the electric ink-based electric heating material provided by the application, at least part of graphene is inserted into vermicular graphite and cooperates with carbon fibers to serve as a framework, so that the electric ink-based electric heating material is low in cost, has excellent heat dissipation performance, is good in flexibility and can resist multiple times of bending; meanwhile, the anti-aging performance is excellent, and the application prospect is wide.
In addition, graphite base electric heat material that this application provided is through introducing graphite alkene for its radiating heat wave has health care effect to the human body when electrical heating.
The type of graphene is not limited, and includes but is not limited to one or more of graphene oxide, hydrogenated graphene, or fluorinated graphene. The preparation method of graphene is also not limited, and includes but is not limited to mechanical exfoliation, CVD (chemical vapor deposition) or epitaxial growth prepared graphene.
In order to further improve the thermal conductivity of the graphite-based electrothermal material, the mass ratio of the vermicular graphite to the graphene is preferably from 100.5 to 8, and particularly, when the mass ratio of the vermicular graphite to the graphene is from 1 to 5.
In order to further improve the bending resistance and strength of the graphite-based electric heating material, the mass ratio of the total mass of the graphene and the vermicular graphite to the carbon fiber is preferably 100.0034-1, and particularly when the mass ratio of the total mass of the graphene and the vermicular graphite to the carbon fiber is 100.0068-0.8, the bending resistance of the graphene electric heating material is more excellent, and the strength and the heat dissipation performance are also higher.
Typically, but not by way of limitation, the mass ratio of vermicular graphite and graphene is 100; typically but not limitatively, the total mass of graphene and vermicular graphite to the mass of carbon fiber is, for example, 100.
In some embodiments of the present application, in order to improve the convenience of application of the graphite-based electric heating material, the graphite-based electric heating material is provided as a strip-shaped graphite-based electric heating film having a density of 1.5 to 2.0g/cm 3 The thickness is 40 μm-2mm. The density of the graphite-based electric heating material is too low, the heat conductivity is small, and the heat dissipation effect is poor; the processing technology is difficult and the cost is high when the density is too high, and the density of the graphite-based electrothermal film is 1.5-2.0g/cm by adjusting the composition of the graphite-based electrothermal film 3 When the graphite-based electrothermal film is used, the graphite-based electrothermal film has more excellent heat dissipation capability under the condition that the processing process cost is not obviously increased, and the density of the graphite-based electrothermal film can be influenced by the change of the processing process on the premise of the same composition, such as the rolling pressure during rolling and the like. The thickness of the graphite-based electrothermal film is too high, the heat conductivity is low, and the heat dissipation effect is poor; the strength is small when the thickness is too low, the bending resistance is poor, and when the thickness of the graphite-based electric heating film is preferably 40 mu m-2mm, the graphite-based film has more excellent strength and heat dissipation performance.When the density of the graphite-based electrothermal film is higher than 2.0g/cm 3 In the process, the graphite-based electrothermal film obtained by the prior art has obvious cracks and delamination phenomena, cannot be applied and has the density lower than 1.5g/cm 3 In the case of graphite films, the thermal conductivity is low and the flexibility is extremely poor. When the thickness of the graphite-based electric heating film is less than 40 mu m, the graphite-based electric heating film obtained by the prior art is difficult to form a flat and uniform film-shaped structure.
Typically, but not by way of limitation, the graphite-based electrothermal film has a density of, for example, 1.5g/cm 3 、1.6g/cm 3 、1.7g/cm 3 、1.8g/cm 3 、1.8g/cm3、1.9g/cm 3 、1.95g/cm 3 Or 2.0g/cm 3 (ii) a The thickness is, for example, 40 μm, 60 μm, 80 μm, 100 μm, 200 μm, 500 μm, 800 μm, 1mm, 1.2mm, 1.5mm, 1.8mm or 2mm.
In some embodiments of the present application, in order to further improve the thermal conductivity and the bending resistance of the graphite-based electrothermal film, it is preferable that the graphene electrothermal film comprises a plurality of layered units, each layered unit comprises graphene and vermicular graphite, the layered units are alternately stacked with carbon fibers, and at least part of the carbon fibers are embedded in the layered units, so as to further improve the compactness and the mechanical strength of the graphite-based electrothermal film.
In another exemplary embodiment of the present application, there is provided a method of manufacturing the graphite-based electric heating material described above, including: step S1, mixing graphene and vermicular graphite to enable at least part of graphene to be inserted into the vermicular graphite to obtain a compound; s2, mixing the carbon fiber product with the compound to obtain a graphite-based electric heating material; the carbon fiber product is made of carbon fibers.
The preparation method of the graphite-based electric heating material is simple in process, large-scale production is easy to realize, and the preparation cost of the graphite-based electric heating material can be effectively reduced. Meanwhile, the graphite-based electric heating material prepared by the preparation method provided by the application has the advantages that at least part of graphene is inserted into the vermicular graphite and is cooperated with the carbon fiber to serve as a framework, so that the cost is low, the heat dissipation performance is excellent, the flexibility is good, the repeated bending resistance is realized, the aging resistance is excellent, and the application prospect is wide. In addition, graphite base electric heat material that this application provided is through introducing graphite alkene for its radiating heat wave has health care effect to the human body when electrical heating.
The graphene may be intercalated into the vermicular graphite, in which the sheet diameter of the graphene is intercalated into the vermicular graphene, or the sheet diameter of the graphene is intercalated into the gap between adjacent vermicular graphene.
The type of the carbon fiber product is not limited, and the carbon fiber product can be carbon fiber yarn or carbon fiber cloth. When the carbon fiber wires are used as the framework, in order to enhance the strength of the graphite-based electric heating material in the transverse and longitudinal directions, the carbon fiber wires are preferably sequentially placed in one direction, and then sequentially placed in the direction perpendicular to the placed carbon fiber wires again, so that the graphite-based electric heating material has excellent bending resistance and mechanical strength in the transverse and longitudinal directions. In order to improve the bending resistance and mechanical strength of the graphite-based electric heating material, the diameter of the carbon fiber wire is preferably 6-8 μm, and when the carbon fiber cloth is used as the skeleton, the density of the carbon fiber cloth is preferably 4mm × 4mm-10mm × 10mm.
Typically, but not by way of limitation, the carbon fiber filaments have a diameter of, for example, 6 μm, 6.5 μm, 7 μm, 7.5 μm, or 8 μm; the density of the carbon fiber cloth is, for example, 4 mm. Times.4 mm, 5 mm. Times.5 mm, 6 mm. Times.6 mm, 7 mm. Times.7 mm, 8 mm. Times.8 mm, 9 mm. Times.9 mm or 10mm. Times.10 mm.
In some embodiments of the present application, in order to further facilitate the insertion of graphene into vermicular graphite, it is preferred that step S1 comprises: mixing the graphene solution and the vermicular graphite to insert at least part of graphene into the vermicular graphite to obtain a composite system; and drying the composite system to obtain the composite. Graphene and vermicular graphite are mixed in a liquid environment, so that the graphene can enter the vermicular graphite more easily.
The mixing method is not limited, and any method capable of inserting the graphene into the vermicular graphite may be used, including but not limited to any one of stirring, kneading and ultrasonic or a combination of at least two methods.
In order to improve the drying efficiency, the temperature of the drying is preferably 20-250 ℃, and the temperature is too high, so that the preparation of the compound with excellent heat-conducting property is not facilitated; the drying time is longer when the temperature is too low, the drying efficiency is lower, and the preferable drying temperature is 20-250 ℃, so that the drying efficiency is improved, and the compact compound combining graphene and vermicular graphite is obtained. Especially when the drying temperature is 80-120 ℃, the drying efficiency is improved under low energy consumption.
The source of the vermicular graphite is not limited, and the vermicular graphite may be commercially available or homemade. The vermicular graphite can be obtained by treating expandable graphite at 500-950 deg.C for 5-60s, or by using "a method for preparing flexible graphite without high temperature expansion" (patent No. CN 108545737A), and the expandable graphite is commercially available from manufacturers such as Qingdao Hengsheng technology Co., ltd.
In order to improve the mixing efficiency of the graphene solution and the vermicular graphite, the mass concentration of the graphene solution is preferably 0.1-8%. The mass concentration of the graphene solution is too high, the graphene is easy to agglomerate, so that the diffusion movement capacity is insufficient, and the efficiency of inserting the graphene into vermicular graphite is low; the mass concentration of the graphene solution is too low, the probability of inserting the graphene into the vermicular graphite is reduced, when the mass concentration of the graphene solution is 0.5% -5%, the graphene can be more favorably inserted into the vermicular graphite, a compact compound combined by the graphene and the vermicular graphite can be obtained, and particularly, when the mass concentration of the graphene is 2% -4%, the compound combined by the graphene and the vermicular graphite can be more favorably obtained, and the heat-conducting property is more excellent. When the concentration of the graphene solution is higher than 8%, the graphene is seriously agglomerated, the amount of the graphene inserted into the vermicular graphite is small, and the obtained composite is uneven, so that local material falling can occur.
The solution of graphene is prepared by dispersing graphene in a solvent, and the type of the solvent is not limited, and any solvent capable of stably dispersing graphene may be used, including but not limited to polyvinylpyrrolidone and the like.
Typically, but not by way of limitation, the solution of graphene has a mass concentration of, for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, or 8%. Typically, but not by way of limitation, when the vermicular graphite is prepared by heat-treating expandable graphite, the heat-treatment temperature is, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃; the heat treatment time is, for example, 5s, 8s, 10s, 15s, 20s, 30s, 40s, 50s or 60s. Typically, but not by way of limitation, the drying temperature of the composite system is, for example, 20 deg.C, 50 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, or 250 deg.C
In order to further improve the compactness of the graphene combined with the vermicular graphite in the composite, the step S1 preferably further comprises the process of rolling the composite to form a composite sheet, and the density of the composite sheet is preferably 0.064-0.44g/cm 3 。
The rolling can be carried out by adopting a roller press or a calender press, and the pressure can be adjusted by adjusting the roller spacing of the roller press or calender press during the rolling process, so that the density of the composite sheet is controlled to be 0.064-0.44g/cm 3 . When the density of the composite sheet is higher than 0.44g/cm 3 In the process, the composite sheet and the carbon fiber product are laminated, so that the use requirement cannot be met. When the density of the composite sheet is less than 0.064g/cm 3 In the process, the vermicular graphene is easy to fly and carbon fiber products are difficult to uniformly distribute, so that the mechanical property cannot meet the use requirement.
Typically, but not by way of limitation, the composite sheet has a density of, for example, 0.064g/cm 3 、0.068g/cm 3 、0.07g/cm 3 、0.08g/cm 3 、0.1g/cm 3 、0.15g/cm 3 、0.2g/cm 3 、0.25g/cm 3 、0.3g/cm 3 、0.35g/cm 3 、0.4g/cm 3 Or 0.44g/cm 3 。
In some embodiments of the present application, in order to further improve the bending resistance and strength of the graphite-based electric heating material, it is preferable that the step S2 includes: and (3) alternately laminating and pressing the carbon fiber products and the compound to obtain the graphite-based electric heating material.
When the carbon fiber products and the composite are alternately stacked, the number of layers of the composite may be adjusted as needed, for example, when the density of the composite is low, at least two layers of the composite may be stacked and then the carbon fiber products may be placed. Furthermore, in order to prepare a graphite-based electric heating material having an appropriate density and thickness, the above pressing may be performed a plurality of times so that the graphite-based electric heating material reaches a corresponding density and thickness.
In a third exemplary embodiment of the present application, an electrothermal apparatus is provided, which includes a heat sink material, the heat sink material being any one of the graphite-based electrothermal materials provided in the first exemplary embodiment of the present application or a graphite-based electrothermal material prepared according to any one of the preparation methods provided in another exemplary embodiment of the present application.
The application provides an electric heating equipment adopts graphite base electric heating material as heat radiation material, and low cost not only has excellent heat conductivity moreover, can also be able to bear or endure to buckle many times and possess excellent mechanical properties simultaneously, can prepare into various shapes according to actual need, more portable and maintenance.
In some embodiments of the present application, in order to further improve the heat dissipation efficiency, it is preferable that the heat dissipation material is electrically connected to the current collector, so as to generate heat through the current collector, and the graphite-based electric heating material dissipates heat, so that the heat dissipation effect of the electric heating device is more excellent.
The material of the current collector is not limited, and any material capable of generating heat when being electrified may be used, including but not limited to an iron-based composite material, such as an iron-copper composite material, a nickel-based composite material, such as a nickel-steel composite material, an aluminum-based composite material, such as an aluminum-iron composite material, an inorganic material, such as a carbon material, silicon carbide, and the like.
The position of the current collector is not particularly limited, and may be set according to the use requirement of the product, for example, the current collector may be disposed on the circumferential direction and the top surface or the bottom surface of the graphite-based electric heating material, and preferably, the current collector is disposed on at least one edge of the graphite-based electric heating material.
In order to further improve the safety performance of the electric heating device, the graphite-based electric heating material is preferably coated by a plastic package film after being electrically connected with the current collector.
The plastic packaging film is not limited in material, and can be used for all resins capable of resisting high temperature of more than 200 ℃ of the electrothermal equipment, including but not limited to a polytetrafluoroethylene film (PTFE film), a polyether ether ketone film (PEEK film), a polyimide film (PI film), a liquid crystal polymer film (LCP film), a polyphenylene sulfide film (PPS film), a polybenzimidazole film (PBI film), a silicon resin film, a polysulfone film (PSU film) and the like.
In order to further improve the safety performance and the convenience of the electric heating device, the electric heating device preferably further comprises a temperature controller, a fuse, a switch and a power supply, the current collector is electrically connected with the power supply, and the temperature controller, the fuse and the switch are arranged on a circuit between the current collector and the power supply.
The shape of the electric heating device is not limited, and it is preferable that the electric heating device is formed in a blanket shape in order to be hung on a wall or laid on the ground.
When the electric heating equipment is used, a live wire and a zero wire are connected to 220V, 380V or other direct currents, the controller is adjusted, the temperature is set to be 20-150 ℃ to be the cut-off temperature, the switch is turned on, the current collector continuously generates heat after power is on, the heat is transferred to the graphite-based electric heating material, and the heat is transferred to the ambient air through the graphite-based electric heating material.
Above-mentioned electrothermal equipment can roll up graphite base electrothermal material on the mass flow body when idle, reduces storage space, and is smaller and more exquisite, portable or deposit more.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The embodiment provides a graphite-based electrothermal film, which is prepared according to the following steps:
(1) Dispersing 2g of graphene oxide in a polyvinylpyrrolidone (PVP) solution to prepare 400mL of a 0.5% graphene oxide solution, wherein the graphene oxide is redox graphene;
(2) Adding 100g of vermicular graphite into a graphene oxide solution for multiple times, stirring by using a stirrer to enable at least part of graphene oxide to be inserted into the vermicular graphite to obtain a composite system, and drying the composite system at 100 ℃ to obtain a composite, wherein the stirring speed is 150r/min, and the stirring time is 20min;
(3) The compound was uniformly spread on a mold having dimensions of 34.6cm x 34.6cm and a controlled surface density of 42.5mg/cm 2 Adjusting the distance between the roller presses to be 3mm, and performing rolling to obtain the product with the density of 0.44g/cm 3 The composite sheet of (1);
(4) Spreading the composite sheet on a mold, placing carbon fiber cloth with warp and weft densities of 5mm multiplied by 5mm and a fiber fineness of 6.9 mu m on the composite sheet, then placing the composite sheet on the carbon fiber cloth to enable the composite sheet and the carbon fiber cloth to be alternately stacked and pressed for multiple times to obtain the carbon fiber cloth with the thickness of 500 mu m and the density of 1.7g/cm 3 The graphite-based electrothermal film of (1), wherein the mass ratio of the composite sheet to the carbon fiber cloth is 100.
Example 2
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the thickness of the graphite-based electrothermal film is 40 microns, and the density of the graphite-based electrothermal film is 1.6g/cm by adjusting the number of alternately laminated composite sheet layers and carbon fiber cloth and adjusting the pressing times 3 The graphite-based electrothermal film.
Example 3
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the number of alternate lamination layers of the composite sheet layers and the carbon fiber cloth is adjusted and the pressing frequency is adjusted to obtain a graphite-based electrothermal film with the thickness of 2mm and the density of 1.6g/cm 3 The graphite-based electrothermal film.
Example 4
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the thickness of the graphite-based electrothermal film is 500 microns, and the density of the graphite-based electrothermal film is 1.5g/cm by adjusting the number of alternately laminated composite sheet layers and carbon fiber cloth and adjusting the pressing times 3 The graphite-based electrothermal film.
Example 5
This embodiment provides a graphite-based electrothermal film, which is similar to that of embodiment 1The difference is that in the step (4), the thickness of 500 mu m and the density of 2.0g/cm are obtained by adjusting the number of the alternately laminated layers of the composite sheet layer and the carbon fiber cloth and adjusting the pressing times 3 The graphite-based electrothermal film.
Example 6
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (2), the amount of graphene oxide is 1g, and the thickness of the prepared graphite-based electrothermal film is 495 μm.
Example 7
The embodiment provides a graphite-based electrothermal film, which is different from that in embodiment 1, in step (2), the amount of graphene oxide is 5g, and the thickness of the prepared graphite-based electrothermal film is 515 μm.
Example 8
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (2), the amount of graphene oxide is 0.5g, and the thickness of the prepared graphite-based electrothermal film is 493 μm.
Example 9
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (2), the amount of graphene oxide is 8g, and the thickness of the prepared graphite-based electrothermal film is 529 μm.
Example 10
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (2), the amount of graphene oxide is 0.3g, and the thickness of the prepared graphite-based electrothermal film is 492 micrometers.
Example 11
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (2), the amount of graphene oxide is 10g, and the thickness of the prepared graphite-based electrothermal film is 539 μm.
Example 12
The embodiment provides a graphite-based electrothermal film, which is different from that of embodiment 1 in that in step (4), adopted carbon fiber products are carbon fiber yarns, and when the carbon fiber yarns are placed, a plurality of carbon fiber yarns are sequentially placed in one direction, the distance between every two adjacent carbon fiber yarns is 0.5cm, then the plurality of carbon fiber yarns are placed in the direction perpendicular to the placed carbon fiber yarns, the distance between every two adjacent carbon fiber yarns in the perpendicular direction is 0.5cm, wherein the fineness of the carbon fiber yarns is 6.9 micrometers, and the using amount of the carbon fiber yarns is the same as that of carbon fiber cloth in embodiment 1.
Example 13
The embodiment provides a graphite-based electrothermal film, which is different from the embodiment 1 in that in the step (4), the usage ratio of the composite sheet to the carbon fiber cloth is 100.
Example 14
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the usage ratio of the composite sheet to the carbon fiber cloth is 100.
Example 15
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the usage ratio of the composite sheet to the carbon fiber cloth is 100.
Example 16
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (4), the usage ratio of the composite sheet to the carbon fiber cloth is 100.
Example 17
This example provides a graphite-based electrothermal film, which is different from example 1 in that, in step (3), the density of the composite sheet obtained after rolling is 0.064g/cm 3 And in the step (4), the carbon fiber cloth is placed after the 6 layers of the composite sheets are placed.
Example 18
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (1), 1g of graphene oxide is dispersed in polyvinylpyrrolidone to prepare a graphene oxide solution with a mass concentration of 8%.
Example 19
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (1), 1g of graphene oxide is dispersed in polyvinylpyrrolidone to prepare a solution of graphene oxide with a mass concentration of 0.1%.
Example 20
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (1), 1g of graphene oxide is dispersed in polyvinylpyrrolidone to prepare a graphene oxide solution with a mass concentration of 5%.
Example 21
The embodiment provides a graphite-based electrothermal film, which is different from embodiment 1 in that in step (1), 1g of graphene oxide is dispersed in polyvinylpyrrolidone to prepare a graphene oxide solution with a mass concentration of 0.05%.
Comparative example 1
This comparative example provides a graphite-based electrothermal film, which is different from example 1 in that step (1) was not performed, and 100g of vermicular graphite was directly mixed with 2g of graphene oxide to obtain a composite.
Comparative example 2
This comparative example provides a graphite-based electrothermal film, which is different from example 1 in that, in step (4), a carbon fiber cloth was not placed on a composite sheet, and the composite sheet was sequentially laminated and pressed a plurality of times to obtain a graphite-based electrothermal film having a thickness of 500 μm and a density of 1.6g/cm 3 The graphite-based electrothermal film.
Test example 1
The graphite-based electrothermal films provided in the above examples and comparative examples were respectively tested for electrical conductivity, electrical resistivity and tensile strength using a laser thermal conductivity meter, a four-probe electrical resistivity meter and a universal meter, and the electrical conductivity, electrical resistivity and tensile strength were measured again after the graphite-based electrothermal films provided in the above examples and comparative examples were bent 100 times, and the results are shown in table 1 below.
TABLE 1
Remarking: the above "-" represents that no test data was obtained.
In the comparative example 1, the local material dropping phenomenon occurs after the graphene oxide is bent for many times because the graphene oxide cannot be uniformly dispersed in the direct mixing process with the vermicular graphite.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the graphite-based electric heating material provided by the application is inserted into the vermicular graphite through at least partial graphene and cooperates with the carbon fibers as a framework, so that the cost is low, the excellent heat dissipation performance is realized, the flexibility is good, the repeated bending resistance can be realized, the aging resistance is excellent, and the wide application prospect is realized.
Test example 2
The graphite-based electrothermal film provided in example 1 was photographed, and the photograph thereof is shown in fig. 1. And SEM test was performed on the graphite-based electrothermal film provided in example 1, as shown in fig. 2. As can be seen from fig. 2, in the graphite-based electrothermal film provided in example 1, a part of graphene is inserted into vermicular graphite.
The graphite-based electrothermal film provided by the embodiment 1 is subjected to cross-section scanning, and as a result, as shown in fig. 3, it can be seen from fig. 3 that in the graphite-based electrothermal film provided by the embodiment 1, carbon fibers are doped in vermicular graphite.
Example 27
The embodiment provides an electric heating device, which is prepared according to the following steps:
(1) Preparing a silicon carbide material into a long sheet to obtain a current collector 10;
(2) The graphite-based electrothermal film 9 provided by the embodiment 1 is connected with a current collector 10 by screws and is connected with a temperature controller 15, a fuse 14, a switch 13 and a power supply (not shown) in series;
(3) And (3) plastically packaging the current collector 10 and the graphite-based electrothermal film 9 by using a polytetrafluoroethylene film 11 to form a heat dissipation area 8, so as to obtain the electric heating equipment.
Fig. 4 is a schematic structural view of the electric heating device provided in this embodiment, and as can be seen from fig. 4, the electric heating device is blanket-shaped and is provided with a product hook 1, so as to be hung indoors and save space. The electric heating equipment is also provided with screw fixing holes 2 so as to be beneficial to fixing the electric heating equipment at a specific indoor position.
The electric heating equipment is also provided with a thermocouple 3, a zero line binding post 4, a thermocouple binding post 5, a live wire binding post 6 and a ground wire binding post 7.
In order to improve the safety of the electric heating device, the electric heating device is further provided with a protective sheet 12, and the protective sheet 12 is disposed between the current collector 10 and the teflon film 11.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A graphite-based electrocaloric material comprising mixed graphene, vermicular graphite and carbon fibers, wherein at least a portion of the graphene is intercalated into the vermicular graphite.
2. The graphite-based electric heating material as claimed in claim 1, wherein the graphite-based electric heating material is a graphite-based electric heating film having a density of 1.5-2.0g/cm 3 The thickness is 40 μm-2mm.
3. The graphite-based electrocaloric material according to claim 1, wherein the mass ratio of the vermicular graphite to the graphene is 100.5-8, preferably 100;
preferably, the mass ratio of the total mass of the graphene and the vermicular graphite to the carbon fibers is 100.
4. The graphite-based electrothermal material of claim 2, wherein the graphene electrothermal film comprises a plurality of layered units, the layered units comprise the graphene and the vermicular graphite, the layered units are alternately stacked with the carbon fibers, and at least some of the carbon fibers are embedded in the layered units.
5. A method of manufacturing a graphite-based electric heating material according to any one of claims 1 to 4, characterized in that the method of manufacturing comprises:
step S1, mixing the graphene and the vermicular graphite to enable at least part of the graphene to be inserted into the vermicular graphite to obtain a composite;
s2, mixing a carbon fiber product with the compound to obtain the graphite-based electric heating material; the carbon fiber product is composed of the carbon fiber.
6. The method according to claim 5, wherein the step S1 includes:
step S11, mixing the graphene solution and the vermicular graphite to enable at least part of graphene to be inserted into the vermicular graphite to obtain a composite system;
s12, drying the composite system to obtain the composite;
preferably, in the step S11, the mass concentration of the graphene solution is 0.1 to 8%, preferably 0.5 to 5%;
preferably, the manner of mixing includes at least one of stirring, kneading, and sonication;
preferably, the vermicular graphite is obtained by treating expandable graphite at 500-950 ℃ for 5-60 s.
7. The method according to claim 4, wherein the step S12 further comprises a process of rolling the composite into a composite sheet, the density of the composite sheetThe degree is preferably 0.064-0.44g/cm 3 。
8. The method for preparing according to any one of claims 4 to 7, wherein the step S2 includes:
alternately laminating and pressing the carbon fiber products and the compound to obtain the graphite-based electric heating material;
preferably, the carbon fiber product is carbon fiber yarn or carbon fiber cloth, the diameter of the carbon fiber yarn is preferably 6-8 μm, and the density of the carbon fiber cloth is preferably 4mm × 4mm-10mm × 10mm.
9. An electric heating device comprising a heat dissipating material, wherein the heat dissipating material is the graphite-based electric heating material according to any one of claims 1 to 4 or the graphite-based electric heating material obtained by the production method according to any one of claims 5 to 8.
10. The electric heating apparatus according to claim 9, further comprising a current collector electrically connected to the graphite-based electric heating material;
preferably, the current collector is disposed on at least one edge of the graphite-based electrocaloric material; preferably, the current collector and the graphite-based electric heating material are coated by a plastic package film;
preferably, the electric heating equipment still includes temperature controller, fuse, switch and power, the mass flow body with the power electricity is connected, just the mass flow body with be provided with on the circuit between the power temperature controller the fuse with the switch.
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