CN107734722B

CN107734722B - Graphene heating sheet and preparation method thereof

Info

Publication number: CN107734722B
Application number: CN201710937950.0A
Authority: CN
Inventors: 白德旭
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-12-31
Filing date: 2015-12-31
Publication date: 2021-04-06
Anticipated expiration: 2035-12-31
Also published as: CN105506812A; CN107675137B; CN107734722A; CN107675137A; CN105506812B

Abstract

The invention relates to a graphene heating sheet, which comprises a flexible substrate, a graphene film and a nano-scale coating circuit, wherein the nano-scale coating circuit is generated by sputtering, a microstructure is introduced on the substrate in the manufacturing process of the nano-scale coating circuit, the microstructure is provided with a plurality of mutually separated and flat raised substrate planes, a printed conductor plane is partially impressed on the raised substrate planes, substrate grooves which extend back to an impressing mould and are respectively provided with two substrate side walls are connected on the side surface of each raised substrate plane in the direction of entering the substrate, the corresponding two adjacent substrate side walls are intersected at the bottom of the substrate groove, the substrate side walls are used as bearing surfaces of the printed conductor side walls, and the substrate side walls extend from the printed conductor side walls in the direction of facing the bottom of the substrate groove; the far infrared radiation emitted by the graphene heating sheet has no harm to a human body, and has good medical health-care effects of improving a body microcirculation system and promoting metabolism.

Description

Graphene heating sheet and preparation method thereof

The invention has the application number of 201511025777.4, the application date of 2015, 12 months and 31 days, the application type of the invention and the application name of the invention is a divisional application of the graphene intelligent clothing.

Technical Field

The invention relates to the field of graphene, in particular to a graphene heating sheet and a preparation method thereof.

Background

Smart apparel has long been used primarily in advanced fields such as aviation and military. In 1989, professor of handsome in japan fused the information science to the material physical properties and functions, and first proposed the concept of smart materials. Since the advent of wearable multimedia computers in MIT (Massachusetts Institute of Technology ) media laboratories in the 90 s of the 20 th century, scholars both at home and abroad began to pay more attention to the study of wearable Technology and smart apparel.

With the increasing standard of living, people's demands for garments are no longer limited to comfort and fashion, but rather desire to be able to achieve personal health care, entertainment or communication with others by wearing the garments. Meanwhile, the development of modern electronic technology, sensing technology, material science and the like also provides multi-disciplinary technical support for the progress of intelligent clothes. Technical developments in different fields provide various methods for the research of intelligent clothes, but the research aiming at the general mode of intelligent clothes design is not common yet. The intelligent clothes are a combination of electronics and fashion industries, but the two industries are unbalanced, the design of the existing intelligent clothes usually focuses on the electronics technology, and the existing intelligent clothes have poor attractiveness and comfort, and have a great relationship with the design mode of the intelligent clothes which is not mature.

The intelligent function of the intelligent clothing developed at present is realized mainly by 3 ways, namely (1) certain intelligent fibers or modified fibers are woven into fabrics or woven into fabrics to ensure that the clothing has intelligent characteristics; (2) microencapsulating some intelligent substances, and processing the intelligent substances on the fabric by dyeing and finishing or coating and other methods; (3) the electronic components are combined with the fabric through a weaving or embedding method to manufacture the intelligent garment.

The invention discloses a temperature-adjusting garment (application number: 201310358761.X), and relates to a temperature-adjusting garment based on variable thermal resistance. The flexible semiconductor thermoelectric array is arranged between a clothing fabric layer and a clothing lining layer, the flexible semiconductor thermoelectric array is connected with an adjustable load through a converter or sequentially connected with a controller and an external power supply connecting piece, and the converter realizes the switching of the connection relation. The temperature regulation adaptability of the invention is strong, the temperature change in a certain range is based on the self thermal resistance change of the clothes, and the energy consumption is not needed, but the heating element flexible semiconductor hot spot array of the invention is composed of semiconductor thermoelectric materials. The semiconductor thermoelectric material is heated based on an electromagnetic radiation mode, and has the defects of low heating speed, small contact range with a body and the like due to heating through electromagnetic radiation; and electromagnetic radiation can cause high-intensity microwave continuous irradiation, so that the rhythm of the heart is accelerated, the blood pressure is increased, the respiration is accelerated, the patient suffers from wheezing, sweating and the like, and the problem of side effect on the human body can be caused after the patient wears the mask for a long time.

Chinese patent document No. CN104902594A (reference 1) discloses an intelligent temperature-control thermal underwear, which is provided with a heating film layer, a temperature control module and a temperature sensor for controlling the heating temperature; the power supply is connected to the heating film layer through the temperature control module, and the heating film layer can be formed by a low-voltage transparent electrothermal film or can be formed by connecting a plurality of low-voltage transparent electrothermal films in series or in parallel through a lead; the low-voltage transparent electrothermal film generates heat after low-voltage direct current is introduced. It does not disclose that the microstructure of the present invention has a plurality of spaced apart, flat, raised substrate planes onto which printed conductor planes are imprinted; substrate grooves which extend back to the imprinting mold and are respectively provided with two substrate side walls are connected to the side surface of the plane of the raised substrate in the direction of entering the substrate, and the corresponding two adjacent substrate side walls are intersected at the bottom of the substrate groove; the substrate side walls serve as support surfaces for the conductor track side walls, which extend from the conductor track side walls in the direction of the base of the associated substrate trench. Chinese patent document No. CN101913598A (reference 2) discloses a method for preparing a graphene thin film, but it does not disclose the microstructure of the present invention, and those skilled in the art cannot obtain the structural features of the "microstructure" and the technical features that the "microstructure" and the fixed structure can be formed in the same process according to the reference 2, and do not have corresponding technical suggestions. The "graphene prepared by mechanical exfoliation and its application in the preparation of graphene/ceramic composite material" (reference 3) relates only to graphene prepared by mechanical exfoliation and its application in the preparation of graphene/ceramic composite material, and does not disclose the structural features of the "microstructure" and the technical features that the "microstructure" and the fixed structure can be formed in the same process, nor does it suggest the corresponding technology. Therefore, the present invention is not obvious from comparison documents 1, 2, 3 and combinations thereof.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a graphene intelligent clothing which is characterized by comprising a temperature monitoring part, a graphene heating sheet prepared by taking polyester, polypropylene or polyamide polymer fiber woven fabric as a substrate and a data collecting and processing part;

the graphene heating sheet comprises a graphene film which is arranged on a flexible substrate and is generated by a solid carbon source sputtering mode on the basis of a small graphene film which is mechanically stripped, and a nano-scale coating circuit which is generated by a sputtering mode by taking the graphene film as a substrate; the intelligent clothing data collection processing part controls the graphene heating sheet of the intelligent clothing to heat based on monitoring data of the temperature detector in the fixed structure on the substrate, wherein the fixed structure used for positioning the temperature detector of the temperature monitoring part and the microstructure used for improving the electric conduction and the adhesive force of the substrate are formed in the same process.

According to a preferred embodiment, the graphene film generated by the solid carbon source sputtering method is a graphene film selected from the generated small graphene films which are mechanically peeled off in advance, the small graphene film is transferred to a temporary flexible substrate to be used as a starting point for inducing growth of the graphene film, and the graphene film is generated on the substrate by the solid carbon source sputtering method with the small graphene film as the starting point.

According to a preferred embodiment, the production flow of the small graphene films generated by mechanical stripping is as follows:

the high-temperature treatment part is connected with the in-situ reduction part, and nitrogen or inert gas is added to carry out high-temperature treatment on the graphite raw material at the treatment temperature of 200-1200 ℃;

the in-situ reduction part is connected with the mechanical stripping part through a first feeding pipeline, receives the graphite raw material treated by the high-temperature treatment part, adds at least one of nitrogen or hydrogen as a reduction medium at the temperature of 200-1200 ℃, reduces the graphene raw material, and sends the treated raw material to the mechanical stripping part;

the dosing part is connected with the mechanical stripping part through a second feeding pipeline and used for storing a surface active additive and continuously dosing the cylindrical cavity of the mechanical stripping part in the process of stripping the graphite raw material by the mechanical stripping part;

the cylindrical cavity of the mechanical stripping part is connected with the in-situ reduction part through a first feeding channel, the cylindrical cavity of the mechanical stripping part is connected with the dosing part through a second feeding channel, a rotating shaft is vertically connected with a rotating cross rod in the cylindrical cavity, a grinding ball is placed in the cylindrical cavity, and the grinding ball is a bead with the diameter of 50-100 mu m and the hardness of the bead is greater than that of graphite; the cylindrical chamber of the mechanical stripping part is connected with the centrifugal separation part through a discharge channel;

after graphite raw materials are added into the cylindrical cavity in the in-situ reduction part and surface active additives are added into the cylindrical cavity by the dosing part (304), the rotating shaft drives a rotating cross rod which is vertically connected with the shaft to stir in the fixed cylindrical cavity, the rotating cross rod drives grinding balls in the cavity to collide and rub with the graphite raw materials in stirring, and van der Waals forces among graphite layers in graphite are disintegrated under the shearing action of the friction force of the grinding balls by the graphite raw materials to obtain a suspension of graphene and graphite;

and the cylindrical chamber of the mechanical stripping part is used for conveying the turbid liquid of graphene and graphite into the centrifugal separation part through the discharge channel, the turbid liquid of graphene is obtained through centrifugal treatment of the centrifugal separation part, and the turbid liquid of graphene is conveyed into the drying part for drying treatment, so that the small graphene film is obtained.

According to a preferred embodiment, the nanoscale coating circuit is formed by performing nanoscale coating sputtering by putting a graphene film adhered to a flexible substrate and attached with a circuit die as a base material into a magnetron sputtering device.

According to a preferred embodiment, the nanoscale-plated circuit is: and sputtering the graphene film adhered to the flexible substrate to generate a copper film, and generating a nano-scale plating circuit in a stamping mode.

According to a preferred embodiment, the sputtering working pressure of the magnetron sputtering instrument in the coating sputtering process is controlled to be 0.13 Pa-0.20 Pa, the temperature of the base material is less than 50 ℃, the distance between a target and the base material is 5 cm-10 cm, the sputtering angle is 5-8 degrees, the sputtering power is 100W-200W, the thickness of the sputtering coating is controlled to be 50nm-300nm, and a structure that the target is sputtered on the base material is adopted.

According to a preferred embodiment, the graphene film adhered to the flexible substrate is placed into a plasma processor, and is pretreated for 60 seconds under the condition of 50 watts of power by adopting oxygen gas, and then is subjected to sputtering treatment, wherein a sputtering target material comprises metal aluminum, copper or silver.

According to a preferred embodiment, the conductive fiber is made into yarn by core-spun and wrapping method, and the yarn is woven into polyester, polypropylene or polyamide polymer fiber fabric.

According to a preferred embodiment, the temperature monitoring part comprises a temperature detector and a distributed A/D acquisition module, and is connected with the data collection and processing part through the optical fiber conductive fiber; the data processing part comprises a single chip microcomputer, a wireless data transmitter, a mobile terminal, a distributed digital input and output module and a power adjusting module, and the data processing part is connected with the graphene heating sheet through the optical fiber wire.

According to a preferred embodiment, the graphene heating sheet, the temperature detection part and the data collection processing part are encapsulated by epoxy resin, and the connection parts of the conductive fibers, the temperature monitoring part, the data collection processing part and the graphene heating sheet are reinforced and waterproof by rubber or plastic.

The graphene intelligent clothing of the invention at least has the following advantages:

(1) because graphite alkene generates heat the piece and possess ultra-thin, light characteristic, consequently it can not exert an influence to the outward appearance of the intelligent dress based on graphite alkene heating.

(2) The infrared radiation generated by the graphene heating sheet has good medical and physical therapy effects. The graphene material can emit far infrared light waves, has almost the same frequency spectrum as a human body, can effectively activate biomolecules such as nucleic acid and protein of cells of the body, and achieves the effects of improving blood circulation, diminishing inflammation and relieving pain.

(3) The graphene heating sheet has a high heating speed. The heat energy generated by the mutual friction and collision of the carbon atoms of the graphene can enable the graphene heating sheet to be heated up rapidly within 3 seconds, and the temperature can be raised to 35 ℃ within 10 seconds, so that the user can feel warm while wearing the graphene heating sheet.

Drawings

FIG. 1 is a schematic diagram of an intelligent apparel function module of the present invention;

FIG. 2 is a schematic structural diagram of a graphene heating sheet according to the present invention;

FIG. 3 is a schematic flow chart of a mechanical stripping method for preparing a small graphene film;

FIG. 4 is a schematic structural diagram of a mechanical peeling part for preparing a small graphene film by a mechanical peeling method according to the present invention;

FIG. 5 shows a graphene film covered with a copper film bonded to a flexible substrate placed in a press;

fig. 6 shows a graphene film provided with three-dimensionally shaped conductor tracks, which results from the embossing process of fig. 5.

List of reference numerals

101: temperature probe 102: distributed a/D acquisition module 103: single chip microcomputer

104: wireless data transmitter 105: the mobile terminal 106: distributed digital input/output module

107: the power conditioning module 108: the graphene heating sheet 201: protective layer

202: nano-scale plating circuit 203: graphene film 204: adhesive film

205: flexible substrate 301: graphite raw material 302: high temperature treatment part

303: in-situ reduction unit 304: medicine adding portion 305: centrifugal separation part

306: drying section 307: graphene film 400: mechanical stripping part

401: cylindrical chamber 402: first feed channel 403: second feed channel

404: rotation shaft 405: the rotating cross bar 406: grinding ball

407: the discharge channel 501: substrate 502: microstructure

503: copper film 504: the imprint mold 505: impression structure

506: a press 507: the printed wiring 508: plane of printed conductors

509: printed conductor sidewall 510: substrate trench 511: substrate trench bottom

512: raised substrate plane 513: substrate sidewall 514: fixing structure

Detailed Description

The following detailed description is made with reference to the accompanying drawings and examples.

As shown in fig. 1, the functional module of the graphene intelligent clothing of the present invention includes: temperature detection portion, graphite alkene generate heat piece 108 and data processing portion. The temperature monitoring part comprises a temperature detector 101 and a distributed A/D acquisition module 102; the data processing part comprises a singlechip 103, a wireless data transmitter 104, a mobile terminal 105, a distributed digital input and output module 106 and a power adjusting module 107. The temperature detector 101 is connected to the distributed a/D acquisition module 102, and is configured to acquire human body temperature data in real time and send the acquired temperature data to the distributed a/D acquisition module 102. The distributed A/D acquisition module 102 is connected with the single chip microcomputer 103 and transmits acquired temperature data to the single chip microcomputer 103. The single chip microcomputer 103 is connected with the heating power adjusting module 107 through a distributed digital input and output module, and is connected with the mobile terminal 105 through the wireless data transmitter 104. The single chip microcomputer 103 compares and analyzes the collected temperature data with the heating temperature set by the mobile terminal 105, and when the temperature is lower than the heating temperature set by the mobile terminal 105, the single chip microcomputer 103 transmits a heating signal to the power adjusting module 107 through the distributed input and output module to control the graphene heating sheet 108 to heat. Meanwhile, the single chip microcomputer 103 sends the real-time temperature of the human body to the mobile terminal 105 through the wireless data transmitter 104. The user can also control the graphene heating sheet 108 to heat according to the real-time condition of the body through the mobile terminal 105.

The intelligent clothing adopts polyester, polypropylene or polyamide polymer fiber fabric, adopts a core-spun and wrapping method to make conductive fibers into yarns, and weaves the yarns into the polyester, polypropylene or polyamide polymer fiber fabric. The temperature monitoring part is connected with the data collecting and processing part through the optical fiber conductive fiber; the data processing part is connected with the graphene heating sheet 108 through the optical fiber lead. And the graphene heating sheet 108, the temperature detection part and the data collection and processing part are encapsulated by epoxy resin. The connection parts of the conductive fibers, the temperature monitoring part, the data collecting and processing part and the graphene heating sheet 108 are reinforced and waterproof by rubber or plastic.

With reference to fig. 1 and fig. 2, the graphene heating sheet 108 of the present invention includes a flexible substrate 205, a graphene film 203 is disposed on the flexible substrate 205, the graphene film 203 is disposed on the flexible substrate 205 through an adhesive film 204, a nano-scale plating circuit 202 generated by sputtering is disposed on the graphene film 203, and the nano-scale plating circuit 202 is electrically connected to the graphene film 203; the nano-scale plating circuit 202 is electrically connected to the conductive fibers and is connected to the data collection and processing unit through the conductive fibers. The graphene film 203 and the nanoscale plating circuit 202 are covered with a protective layer 201, and the protective layer 201 covers the connection part of the nanoscale plating layer and the conductive fiber.

The structure of the electric heating film with the structure can be prepared by the following processes, and specifically comprises the following steps: providing a flexible substrate 205, and coating an adhesive film 204 on the flexible substrate 205; the material of the flexible substrate 205 includes a PET film, and in order to improve the adhesion of the flexible substrate 205 to the printing surface, a corona treatment or a chemical etching sanding treatment is performed on the printing surface of the flexible substrate 205, and then the adhesive film 204 is coated on the printing surface of the flexible substrate 205. Transferring the graphene film 203 onto a flexible substrate 205, the graphene film 203 being connected to the flexible substrate 205 by an adhesive film 204; sputtering the graphene film 203 to generate a nanoscale plating circuit 202; electrodes are printed on the aforementioned nano-scale plated circuit 202, and the electrodes are used to electrically connect the nano-scale plated circuit 202 with the conductive fibers. A protective layer 201 is printed on the electrode, and the protective layer 201 covers the electrode, the graphene film 203 and the nanoscale plating circuit 202. The protective layer 201 has scratch resistance.

Install flexible substrate 205 on unreeling equipment with the mode of whole book, in succession, the equidistance can be removed the printing position, realizes accurate counterpoint through color mark sensor, can carry out the overprinting of a plurality of patterns, and after printing, flexible substrate 205 gets into the rotation type oven, carries out the rolling after abundant infrared drying and is used for as intelligent dress heating plate.

Because graphite alkene generates heat piece 108 possesses ultra-thin, light characteristic, consequently it can not exert an influence to the outward appearance of the intelligent dress based on graphite alkene heating. The infrared radiation generated by the graphene heating sheet 108 has good medical and physical therapy effects. The graphene material can emit far infrared life light waves, and after the far infrared rays are absorbed by a human body, water molecules in the body can resonate, so that the water molecules are activated, the intermolecular binding force of the water molecules is enhanced, biological macromolecules such as protein and the like are activated, and biological cells are at the highest vibration energy level. Because the biological cells generate resonance effect, the far infrared heat energy can be transferred to the deeper part of the human skin, the temperature of the lower deep layer rises, and the generated heat is emitted from inside to outside. The strength of the action can expand blood capillary, promote blood circulation, strengthen metabolism among tissues, increase regeneration capacity of tissues, improve immunity of organisms and regulate mental abnormal excitation state, thereby playing a role in medical care. Generally, infrared rays emitted from fuel combustion, heat sources of electric heating appliances and the like are near infrared rays, and since the wavelengths are short, a large amount of heat effect is generated, and after the infrared rays irradiate a human body for a long time, the skin and eye crystal are burnt. Other electromagnetic waves with shorter wavelength, such as ultraviolet rays, X-rays, gamma rays and the like, can cause electrons on atoms to be dissociated, and have more harm to human bodies. Far infrared rays are not harmful to burns when used because of their relatively low energy due to their relatively long wavelength.

Far infrared rays are different from low-frequency electromagnetic waves emitted by household appliances, and the low-frequency electromagnetic waves emitted by the household appliances can penetrate through walls and change the characteristics of human body current, so that the harmfulness of the low-frequency electromagnetic waves is highly suspected. The far infrared ray has a penetrating power of only 0.01 to 0.1 cm in human skin, and the human body itself emits far infrared rays having a wavelength of about 9 μm, so that it is not mixed with low frequency electromagnetic waves. Far infrared rays are used for the adjuvant therapy of many diseases, such as muscle and bone muscular soreness, tendonitis, bedsores, scalds, wounds which are not easy to heal, and the like, and the purpose of adjuvant therapy can be achieved by utilizing the characteristic of far infrared rays for promoting blood circulation.

The preparation method of the large-area graphene film comprises the steps of selecting a small graphene film 307 from graphene films generated by mechanical stripping in advance, placing the selected small graphene film 307 on a substrate suitable for a specific application technology of the graphene film, and growing the graphene film 203 on a temporary flexible substrate by using carbon atoms released from a solid carbon source material containing the carbon atoms.

The small graphene film 307 is selected from graphene films produced by a micro-mechanical lift-off method. The shape of the graphene film sheet for inducing the growth of the graphene film is square, rectangular, circular, oval or irregular; the number of layers of the graphene film sheets for inducing the growth of the graphene film is 1 to 200, preferably 1 to 20, and most preferably 1 to 5; the area of the small graphene film 307 as the growth inducing graphene film was 1nm²To 50000cm²Most preferably 1nm²To 1000cm²Most preferably 1nm²To 100 μm². The substrate material is an inorganic or organic conductor, a semiconductor, an insulator or a composite material thereof which is suitable for the specific application technology of the graphene film. The number of layers of the graphene film grown on the substrate is 1 to 200, preferably 1 to 20, and most preferably 1 to 5.

The nano-scale plating circuit 202 is formed by placing a graphene film 203 adhered to a flexible substrate 205 and attached with a circuit die as a base material into a magnetron sputtering device for nano-scale plating sputtering. The flexible substrate 205 with the circuit pattern attached thereto was subjected to a pretreatment for 60 seconds with oxygen at a power of 50 watts. The sputtering working pressure of the magnetron sputtering instrument is controlled to be 0.13 Pa-0.20 Pa in the sputtering process of the coating, the temperature of the base material is less than 50 ℃, the distance between the target and the base material is 5 cm-10 cm, the sputtering angle is 5-8 degrees, the sputtering power is 100W-200W, the thickness of the sputtering coating is controlled to be 50nm-300nm, and a structure that the base material is arranged on the target material is adopted. The material of the nano-scale plated circuit 202 includes aluminum, copper, or silver, and the nano-scale plated circuit 202 has a frame structure formed by a plurality of lines. The electrothermal film material composed of the nanoscale plating circuit 202 and the graphene film 203 has the characteristics of small thickness and high flexibility. The graphene film 203 is a two-dimensional crystal structure with a honeycomb hexagon and formed by single-layer carbon atoms, and is combined with the nano-scale plating circuit 202 with good flexibility, the nano-scale plating circuit 202 enhances the connectivity of graphite and graphite, fills grids among all blanks, can ensure good conductivity of the electrothermal film material, and has light weight and low price. The material of the flexible substrate 205 includes pet (polyethylene terephthalate). The graphene film 203 and the nano-scale plating circuit 202 can generate the required heating heat.

As shown in fig. 3 and 4, the apparatus for forming a graphene film by mechanical exfoliation according to the present invention includes a high temperature treatment unit 302, an in-situ reduction unit 303, a chemical feeding unit 304, a mechanical exfoliation unit 400, a centrifugal separation unit 305, and a drying unit 306. The high-temperature treatment part 302 is connected with the in-situ reduction part 303, and the high-temperature treatment part 302 performs high-temperature treatment on the graphite raw material 301 added therein and sends the treated graphite raw material 301 to the in-situ reduction part 303. The high-temperature treatment temperature is 200-1200 ℃, and the treatment environment is kept as air, vacuum, nitrogen or inert gas. One preferred embodiment is to maintain the process environment as an inert gas environment during the high temperature process. The graphite raw material 301 is heated to 200 ℃ to 1200 ℃ under the protection of inert gas, the stability of the oxygen-containing functional group is reduced, and the oxygen-containing functional group leaves in the forms of water vapor, carbon dioxide and the like. The in-situ reduction unit 103 is connected to the high-temperature treatment unit 302 and the mechanical peeling unit 400. The in-situ reduction unit 303 receives the graphite material 301 treated by the high-temperature treatment unit 302, reduces the graphite material, and sends the treated graphite material 301 to the mechanical separation unit 400. In the in-situ reduction part 303, at least one of nitrogen and hydrogen is added as a reduction medium at a temperature of 200 ℃ to 1200 ℃ to reduce the graphite raw material 301, thereby further removing oxygen-containing functional groups in the graphite raw material 301. The medicated portion 304 is connected to the mechanical peel portion 400. The medicine adding part 304 is used for storing the surface active additive, and continuously adding the medicine to the mechanical peeling part 400 in the process that the mechanical peeling part 400 peels the graphite raw material 301. The surface active additive is one or more of sodium dodecyl sulfate, methyl amyl alcohol, sodium oxalate, sodium methyl cellulose, polyacrylamide, Guel gum and fatty acid polyglycol ester. The mechanical peeling section 400 is connected to the centrifugal separation section 305. The mechanical stripping part 400 is used for receiving the graphite raw material 301 subjected to reduction treatment in the in-situ reduction part 303 and the surfactant provided by the chemical adding part 304, stirring, ball-milling and stripping the received graphite raw material 301, and sending a mixed suspension of graphene and graphite subjected to stripping treatment to the centrifugal separation part 305. The centrifugal separation section 305 is connected to a drying section 306. The centrifugal separation section 305 performs centrifugal processing on the mixed suspension of graphene and graphite introduced therein to obtain a graphene suspension, and sends the graphene suspension to the drying section 306. The drying unit 306 performs a drying process on the graphene suspension entering the drying unit, and finally obtains a graphene film 307.

FIG. 4 is a schematic view of the mechanical stripping section of the present invention. Referring to fig. 2, the mechanical peeling section 400 includes a cylindrical chamber 401, a first feed channel 402, a second feed channel 403, a rotating shaft 404, a rotating crossbar 405, and grinding balls 406. The cylindrical cavity 401 of the mechanical stripping part 400 is connected with the in-situ reduction part 303 through a first feeding channel 402, the cylindrical cavity 401 of the mechanical stripping part 400 is connected with the medicine adding part 304 through a second feeding channel 403, a rotating shaft 404 is vertically connected with a rotating cross rod 405 in the cylindrical cavity 401, and a grinding ball 406 is arranged in the cylindrical cavity 401, wherein the grinding ball 406 is a bead with the diameter of 50-100 μm and the hardness of the bead is greater than that of graphite. The cylindrical chamber 401 of the mechanical stripping section 400 is connected to the centrifugal separation section 305 via a discharge channel 407. The in-situ reduction part 303 feeds the graphite raw material 301 into the cylindrical chamber 401 of the mechanical peeling part 400 through the first feed passage 402. The medicine adding portion 304 adds the surface active additive to the cylindrical chamber 401 of the mechanical peeling portion 400 through the second feed opening 403. The rotating shaft 404 causes a rotating cross bar 405, which is vertically connected to the rotating shaft 204, to agitate within the cylindrical chamber 401. The grinding balls 406 in the cylindrical chamber 401 and the graphite raw material 301 are driven to collide and rub with each other by the rotating cross rod 405 in stirring, and van der waals force among graphite layers in graphite is broken down by the graphite raw material 301 under the shearing action of the friction force of the grinding balls 406, so that turbid liquid of graphene and graphite is obtained.

Example 1

The production process of the graphene film by the mechanical peeling method of the present invention is described with reference to fig. 3 and 4. The high-temperature treatment unit 302 is connected to the in-situ reduction unit 303, and the high-temperature treatment unit 302 performs high-temperature treatment on the graphite raw material 301 added thereto at a high temperature of 1000 ℃ for 1 hour in an inert gas treatment environment, and sends the treated graphite raw material 301 to the in-situ reduction unit 303. The graphite feed 301 is heated to 1000 ℃ under the protection of inert gas, the oxygen-containing functional groups decrease in stability, and leave the graphene feed 301 as water vapor, carbon dioxide, or the like. The in-situ reduction part 303 is connected to the high-temperature treatment part 302 and is connected to the cylindrical chamber 401 of the mechanical peeling part 400 through a first feed passage 402. The in-situ reduction unit 303 receives the graphite raw material 301 treated by the high-temperature treatment unit 302, and performs a reduction treatment for 1 hour by adding at least one of nitrogen and hydrogen as a reduction medium at a temperature of 1000 ℃, and the treated graphite raw material 301 is sent to the cylindrical chamber 401 of the mechanical peeling unit 400. The graphite raw material 301 is subjected to a reduction treatment to further remove the oxygen-containing functional groups in the graphite raw material 301. The medicated portion 304 is connected to the cylindrical chamber 401 of the mechanical peel portion 400 through a second feed channel 403. The medicine adding part 304 is used for storing a surface active additive, and in the process of stripping the graphite raw material 301 by the mechanical stripping part 400, sodium dodecyl sulfate and water are continuously added into the mechanical stripping part 400 to prepare slurry with the concentration of 80.0%. The rotating shaft 404 of the mechanical peeling part 400 is vertically connected with the rotating cross bar 405 in the cylindrical chamber 401, the grinding balls 406 are placed in the cylindrical chamber 401, and the in-situ reduction part 303 adds the graphite raw material 301 to the cylindrical chamber 201 of the mechanical peeling part 200 through the first feeding passage 402. The medicine adding portion 304 adds the surface active additive to the cylindrical chamber 401 of the mechanical peeling portion 400 through the second feed opening 403. The rotating shaft 404 causes a rotating cross bar 405, which is vertically connected to the rotating shaft 404, to agitate within the cylindrical chamber 401. The grinding balls 406 in the cylindrical chamber 401 and the graphite raw material 401 are driven to collide and rub with each other by the rotating cross rod 405 in stirring, and van der waals force among graphite layers in graphite is broken down by the graphite raw material 301 under the shearing action of the friction force of the grinding balls 406, so that turbid liquid of graphene and graphite is obtained. The grinding balls 406 are beads having a diameter of 50-100 μm and a hardness greater than that of graphite. In the grinding ball 406 of this embodiment, the grinding ball with a diameter of 50 μm to 100 μm is used as the ball milling medium, and in the mechanical graphite stripping process, the number of times that the graphite sheet layer is repeatedly stripped is significantly increased compared to the ball milling medium with a diameter greater than 100 μm, thereby improving the mechanical stripping efficiency. And the thickness distribution of the obtained graphite flake layers is concentrated, and more than 50% of the graphite flake layers are all below 4 nm.

The cylindrical chamber 401 of the mechanical stripping section 400 is connected to the centrifugal separation section 305 via a discharge channel 407. The mechanical peeling unit 400 sends the mixture suspension of graphene and graphite subjected to the peeling process to the centrifugal separation unit 305 through the discharge passage 407. The centrifugal separation section 305 is connected to a drying section 306. The centrifugal separation section 305 performs centrifugal processing on the mixed suspension of graphene and graphite introduced therein to obtain a graphene suspension, and sends the graphene suspension to the drying section 306. The drying unit 306 performs a drying process on the graphene suspension entering the drying unit, and finally obtains a graphene film 307.

Example 2

Referring to fig. 2 and fig. 3, a single-layer graphene prepared by a mechanical peeling method is used as a graphene platelet for inducing large-area growth of graphene, and the graphene platelet 307 is transferred to a temporary growth flexible substrate copper foil to induce growth of a graphene film 203. And (3) placing the copper foil substrate with the graphene film small pieces in a sputtering chamber, and sputtering carbon atoms on the copper foil substrate from a solid carbon source target by adopting laser pulses, so that the graphene film 203 grows on the copper foil substrate by taking the graphene film small pieces as starting points.

Then, the graphene film 203 is transferred onto the flexible substrate 205 by adopting a chemical etching and transfer method, in order to separate the graphene film 203 from the temporary substrate, the adhesive film 204 on the flexible substrate 205 comprises PVB or ethyl cellulose, and the like, and the graphene film 203 on the temporary substrate is laminated with the adhesive film 204 on the flexible substrate 205 to form a temporary bonding body; the temporary substrate is removed to obtain the graphene film 203 on the flexible substrate 205. After the graphene film 203 is bonded to the flexible substrate 205, the copper foil or the nickel foil serving as a temporary substrate needs to be separated, so that the graphene film 203 grown on the copper foil is completely transferred to the target flexible substrate 205. The graphene film 203 prepared by the method has high purity and large area.

The nano-scale plating circuit 202 is formed by placing a graphene film 203 adhered to a flexible substrate 205 and attached with a circuit die as a base material into a magnetron sputtering device for nano-scale plating sputtering. The graphene film 203 attached with the circuit mold and adhered to the flexible substrate 205 was subjected to pretreatment for 60 seconds with oxygen at a power of 50 watts. The sputtering working pressure of the magnetron sputtering instrument is controlled to be 0.13Pa, the substrate temperature is 25 ℃, the distance between the target and the substrate is 5cm, the sputtering angle is 8 degrees, the sputtering power is 100W, the sputtering target material is metal copper, the thickness of the sputtering coating is controlled to be 50nm-300nm, the structure that the substrate is arranged above the sputtering target material is adopted, the circuit die is taken down after the sputtering is finished, and the coating circuit is prepared. Electrodes are printed on the aforementioned nano-scale plated circuit 202, and the electrodes are used to electrically connect the nano-scale plated circuit 202 with the conductive fibers. A protective layer 201 is printed on the electrode, and the protective layer 201 is made of epoxy resin and has waterproof and scratch-proof capabilities. The protective layer 201 covers the electrodes and covers the graphene film 203 and the nanoscale plating circuit 202.

Example 3

With reference to fig. 2, 3, 5 and 6, a single-layer graphene prepared by a mechanical peeling method is used as a graphene platelet for inducing large-area growth of graphene, and the graphene platelet 307 is transferred to a temporary growth flexible substrate copper foil to induce growth of a graphene film 203. And (3) placing the copper foil substrate with the graphene film small pieces in a sputtering chamber, and sputtering carbon atoms on the copper foil substrate from a solid carbon source target by adopting laser pulses, so that the graphene film 203 grows on the copper foil substrate by taking the small graphene film 307 as a starting point.

Then, the graphene film 203 is transferred onto the flexible substrate 205 by adopting a chemical etching and transfer method, in order to separate the graphene film 203 from the temporary substrate, the adhesive film 204 on the flexible substrate 205 comprises PVB or ethyl cellulose, and the like, and the graphene film 203 on the temporary substrate is laminated with the adhesive film 204 on the flexible substrate 205 to form an adhesive body; and removing the temporary substrate copper foil to obtain the graphene film 203 on the flexible substrate 205. After the graphene film 203 is bonded to the flexible substrate 205, the copper foil serving as a temporary substrate needs to be separated, so that the graphene film 203 grown on the copper foil is completely transferred to the target flexible substrate 205. The graphene film 203 prepared by the method has high purity and large area.

The manufacturing process of the nanoscale plating circuit 202 is as follows: the graphene film 203 adhered to the flexible substrate 205 is put into a magnetron sputtering device as a substrate 501 for nano-scale plating sputtering, the substrate 501 coated with the copper film 503 by sputtering is sent into a press 506, and under the action of an imprint mold 504, two copper films 503 which are separated from each other and have different sizes are laminated on the substrate 501. The imprint template 504 not only provides an imprint structure 505 in the region above the copper film 503, but also has an imprint structure 505 in the region outside the film 503, and can introduce the microstructure 502 shown in fig. 6, in particular a fluid microstructure 502, into the substrate 501. The imprinting mold 504 simultaneously forms a fixed structure 514 on the substrate 501, the fixed structure 514 can be used for fixing the temperature detector 101 of the temperature monitoring part, the intelligent clothing data collecting and processing part controls the heating of the graphene heating sheet 108 of the intelligent clothing based on the monitoring data of the temperature detector 101 from the fixed structure 514, wherein the fixed structure 514 for positioning the temperature monitoring part and the microstructure 502 of the substrate 501 are formed in the same process, and the forming process of the fixed structure 514 and the microstructure 502 is formed in one imprinting process of the imprinting mold 504, so that in the industrial production process, the rapid forming of the fixed structure 514 and the microstructure 502 is realized, and the production speed of the nano-scale plating circuit 202 is improved. As shown in fig. 6, the copper film 503 forms three-dimensionally shaped, mutually insulated conductor tracks or circuits. Each conductor track 507 has a flat conductor track plane 508 which is arranged convexly with respect to the microstructure 502 and extends into the drawing plane, and at least one conductor track side wall 509 which is arranged at an angle to the conductor track plane 508. Depending on the arrangement of the conductor tracks 507 on the substrate 501, and more precisely depending on the arrangement of the imprinted microstructures 502, it can be seen that a single conductor track plane 508 either has a single conductor track side wall 509 or has two conductor track side walls 509 spaced apart from one another transversely to the longitudinal extension of the conductor tracks 507. The conductor track sidewalls 509 extend into the substrate trenches 510 of the microstructures 502 (i.e., in a direction away from the imprint mold), but do not reach the corresponding substrate trench bottoms 511. As shown in fig. 6, each two adjacent conductor tracks 508 are arranged at least approximately at the same height or plane and are electrically insulated from one another by a transverse spacing.

As shown in fig. 6, the microstructure has a plurality of spaced-apart, flat, raised substrate planes 512 (raised substrate portions), wherein printed conductor planes 508 (raised printed conductor portions) are impressed on top of the raised substrate planes 512. On the side of the raised substrate plane 512, substrate trenches 510 each having two substrate sidewalls 513 extending away from the imprint mold are connected in the direction into the substrate 501. Respective two adjacent substrate sidewalls 513 intersect at the substrate trench bottom 511. The substrate sidewalls 513 serve as support surfaces for the conductor track sidewalls 509, wherein the substrate sidewalls 513 extend from the conductor track sidewalls 509 in the direction of the associated substrate trench bottom 511.

In the region between two adjacent, mutually opposite side walls 509 of the conductor tracks, no residual copper film 503 is present on the substrate 501. This does not result in the removal of the remaining copper film segment 503 from the substrate 501 after the imprinting process. All the copper film 503 is thus electrically available, the printed conductor cross section is enlarged and the current-carrying capacity is increased.

The printed conductors are printed with electrodes to form the nano-scale plated circuit 202, and more specifically, the printed conductors connected by the electrodes form a nano-scale plated parallel circuit, and the nano-scale plated circuit 202 is electrically connected to the conductive fibers through the electrodes. The protective layer 201 is printed on the electrode, and the protective layer 201 is made of epoxy resin and has insulating, waterproof and scratch-resistant capabilities. The protective layer 201 covers the electrodes and covers the graphene film 203 and the nanoscale plating circuit 202. Because the graphene film 203 has the microstructure 502, the surface area of the graphene film 203 is enlarged, the bonding strength between the protective layer 201 and the graphene film is increased, the protective effect is improved, meanwhile, the contact tightness between the nanoscale coating circuit 202 and the graphene film 203 is improved, and the conductivity of the graphene film 203 is increased.

It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents.

Claims

1. The preparation method of the graphene heating sheet is characterized in that the graphene heating sheet (108) is prepared according to the following steps:

providing a flexible substrate (205) and coating an adhesive film (204) on the flexible substrate (205); transferring the graphene film (203) onto a flexible substrate (205), the graphene film (203) being connected to the flexible substrate (205) by an adhesive film (204);

sputtering a nano-scale plating circuit (202) on the graphene film (203);

printing electrodes on the nano-scale plating circuit (202), wherein the electrodes are used for realizing the electrical connection between the nano-scale plating circuit (202) and the conductive fibers;

printing a protective layer (201) on the electrode, wherein the protective layer (201) covers the electrode and covers the graphene film (203) and the nanoscale coating circuit (202);

in order to improve the adhesion of a printing surface required to be formed on the flexible substrate (205), performing corona treatment or chemical corrosion sanding treatment on the printing surface of the flexible substrate (205), and then coating an adhesive film (204) on the printing surface of the flexible substrate (205);

wherein microstructures (502) for improving electrical conductivity and adhesion are introduced onto a substrate (501) during the fabrication of the nano-scale plated circuit (202), the microstructure (502) having a plurality of spaced apart, flat raised substrate planes (512), -partial imprinting of a printed conductor plane (508) on top of said raised substrate plane (512), on the side of the raised substrate plane (512), substrate trenches (510) each having two substrate side walls (513) extending away from the imprint mold are connected in the direction of entry into the substrate (501), the respective two adjacent substrate side walls (513) intersecting at the associated substrate trench bottom (511), the substrate side walls (513) serve as bearing surfaces for the conductor track side walls (509), the substrate side walls (513) extend from the conductor track side walls (509) in the direction of the substrate trench bottom (511);

the method comprises the steps that a graphene film (203) generated by a solid carbon source sputtering mode is a small graphene film (307) selected from small graphene films generated by mechanical stripping in advance, the small graphene film (307) is transferred onto a temporary flexible substrate to serve as a starting point for inducing growth of the graphene film (203), and the graphene film (203) is generated on the temporary flexible substrate by a solid carbon source sputtering mode with the small graphene film (307) serving as the starting point;

wherein the production flow of the small graphene film (307) generated by mechanical stripping is as follows:

the high-temperature treatment part (302) is connected with the in-situ reduction part (303), and nitrogen or inert gas is added to carry out high-temperature treatment on the graphite raw material (301) at the treatment temperature of 200-1200 ℃;

the in-situ reduction part (303) is connected with the mechanical stripping part (400) through a first feeding channel (402), receives the graphite raw material (301) processed by the high-temperature processing part (302), adds at least one of nitrogen or hydrogen as a reduction medium at the temperature of 200-1200 ℃, reduces the graphene raw material (301), and sends the processed raw material to the mechanical stripping part (400);

the medicine adding part (304) is connected with the mechanical stripping part (400) through a second feeding channel (403), the medicine adding part (304) is used for storing a surface active additive, and continuously adding medicine into a cylindrical cavity (401) of the mechanical stripping part (400) in the process that the mechanical stripping part (400) strips the graphite raw material (301);

the cylindrical cavity (401) of the mechanical stripping part (400) is connected with the in-situ reduction part (303) through a first feeding channel (402), the cylindrical cavity (401) of the mechanical stripping part (400) is connected with the medicine adding part (304) through a second feeding channel (403), a rotating shaft (404) is vertically connected with a rotating cross rod (405) in the cylindrical cavity (401), a grinding ball (406) is placed in the cylindrical cavity (401), and the grinding ball (406) is a bead with the diameter of 50-100 mu m and the hardness of the bead is larger than that of graphite; the cylindrical chamber (401) of the mechanical stripping section (400) is connected to the centrifugal separation section (305) via a discharge channel (407);

after the graphite raw material (301) is added into the cylindrical cavity (401) through the in-situ reduction part (303) and the surface active additive is added into the cylindrical cavity (401) through the dosing part (304), the rotating shaft (404) drives a rotating cross rod (405) which is vertically connected with the shaft to stir in the fixed cylindrical cavity (401), the rotating cross rod (405) drives grinding balls (406) in the cavity and the graphite raw material (301) to collide and rub with each other in stirring, and van der waals force among graphite layers in graphite is decomposed under the shearing action of the friction force of the grinding balls by the graphite raw material (301) to obtain a suspension of graphene and graphite;

the cylindrical chamber (401) of the mechanical stripping part (400) sends the graphene and graphite suspension to a centrifugal separation part (305) through a discharge channel (407), the graphene suspension is obtained through centrifugal treatment of the centrifugal separation part (305), and the graphene suspension is sent to a drying part (306) for drying treatment, so that small graphene films (307) are obtained.

2. The method of claim 1, wherein the nanoscale-plated circuit (202) is fabricated by:

putting the graphene film (203) adhered to the flexible substrate (205) as a substrate (501) into a magnetron sputtering device for nano-scale plating sputtering;

feeding the substrate (501) coated with the copper film (503) by sputtering into a press (506);

laminating two copper films (503) which are separated from each other and have different sizes on the substrate (501) under the action of an imprinting mould (504);

wherein the imprint template (504) is provided with an imprint structure (505) not only in the region above the copper film (503), but also in a region outside the copper film (503) with an imprint structure (505) for introducing the microstructure (502) into the substrate (501), the imprint template (504) simultaneously forming a fixing structure (514) on the substrate (501), the fixing structure (514) being capable of being used for fixing the temperature detector (101) of the temperature monitoring portion.

3. The preparation method of claim 2, wherein the sputtering pressure of the magnetron sputtering apparatus during the sputtering process of the coating is controlled to be 0.13Pa to 0.20Pa, the temperature of the substrate is less than 50 ℃, the distance between the target and the substrate is 5cm to 10cm, the sputtering angle is 5 degrees to 8 degrees, the sputtering power is 100W to 200W, and the thickness of the sputtered coating is controlled to be 50nm to 300 nm.

4. The method of claim 2, wherein the graphene film (203) adhered to the flexible substrate (205) is subjected to a plasma treatment using oxygen gas at a power of 50 watts for 60 seconds followed by a sputtering process, wherein the sputtering target comprises aluminum, copper or silver.

5. A graphene heating sheet, wherein the graphene heating sheet is prepared according to the preparation method of one of claims 1 to 4.