CN115678062A - Graphene heating film and preparation method thereof - Google Patents
Graphene heating film and preparation method thereof Download PDFInfo
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- CN115678062A CN115678062A CN202211217379.2A CN202211217379A CN115678062A CN 115678062 A CN115678062 A CN 115678062A CN 202211217379 A CN202211217379 A CN 202211217379A CN 115678062 A CN115678062 A CN 115678062A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 163
- 238000010438 heat treatment Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000004005 microsphere Substances 0.000 claims abstract description 47
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 claims abstract description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 37
- 229960003638 dopamine Drugs 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 20
- 239000012065 filter cake Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005002 finish coating Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical field of lithium battery thermal management components, and particularly relates to a graphene heating film and a preparation method thereof. The product developed by the invention comprises a waterborne polyurethane adhesive and graphene dispersed in the polyurethane adhesive; the graphene comprises two graphene particles with different morphologies; the graphene particles with different morphologies are respectively a layered graphene sheet and a spherical or spheroidal graphene microsphere; the particle size distribution of the graphene microspheres is 80-120nm; the particle size distribution of the graphene sheets is 20-50nm; the mass ratio of the graphene microspheres to the graphene sheets is 3:4-3:7. in addition, the OI value of the graphene heating film is 45-60; the OI value is as follows: adopting XRD diffraction to obtain a diffraction pattern, and then adopting the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 peak in the pattern as an OI value; the graphene microspheres are hollow graphene microspheres.
Description
Technical Field
The invention belongs to the technical field of lithium battery thermal management components. More particularly, the invention relates to a graphene heating film and a preparation method thereof.
Background
For lithium ion batteries, especially lithium iron phosphate batteries, the performance of the batteries can be effectively exerted only by heating the batteries in a low-temperature environment in winter. In the traditional electric heating field, electric heating materials are mainly divided into two categories: metal resistance wires and ceramic heating materials. The metal resistance wire has the defects of high density, easy oxidation, low heat conversion efficiency, serious electromagnetic radiation and the like; and the alloy has poor processability and is not suitable for being used in the lithium battery environment. The ceramic heating material has the disadvantages of slow heating rate, great brittleness and poor anti-seismic performance. Therefore, the research on the novel hot materials with the advantages of good flexibility, uniform heating, high electrothermal conversion efficiency and the like has profound significance for the long-term development of the lithium iron phosphate battery.
Graphene has the characteristics of good electric and heat conducting properties, large specific surface area, high mechanical strength and the like, and is continuously applied to the fields of miniature electronic equipment, energy storage, composite materials and the like. Although highly conductive and highly elastic graphene composite materials can be prepared by using graphene. However, the graphene sheets obtained by the conventional manufacturing process are directly used as the main functional filler of the heating film, and not only the dispersion uniformity of the graphene sheets in the matrix is considered, but also a continuous heat-conducting network can be formed among different graphene sheets, which is a spear per se, so that the graphene heat-conducting film has good dispersion performance, and the connection probability between the sheets is greatly reduced, so that how to take account of the dispersion of the filler, and ensure a good heat-conducting network structure is one of the technical problems in manufacturing the graphene heat-conducting film.
Disclosure of Invention
The invention aims to overcome the defects that the conventional heating film product for the heat management of the lithium battery is difficult to realize uniform and high-efficiency heat conductivity, and provides a graphene heating film and a preparation method thereof.
The invention aims to provide a graphene heating film.
The invention also aims to provide a preparation method of the graphene heating film.
The above purpose of the invention is realized by the following technical scheme:
a graphene exothermic film, comprising: the adhesive comprises a waterborne polyurethane adhesive and graphene dispersed in the polyurethane adhesive;
the graphene comprises two graphene particles with different morphologies;
the graphene particles with different morphologies are respectively a layered graphene sheet and a spherical or spheroidal graphene microsphere;
the particle size distribution of the graphene microspheres is 80-120nm; the particle size distribution of the graphene sheets is 20-50nm;
the mass ratio of the graphene microspheres to the graphene sheets is 3:4-3:7.
according to the technical scheme, the waterborne polyurethane is used as the adhesive, spherical or spherical-like graphene microspheres with relatively large particle sizes are bonded with the layered graphene sheets to obtain the continuous graphene heating film, and the addition amount of the graphene microspheres is limited to be less than that of the graphene sheets.
Firstly, after spherical or spheroidal graphene microspheres with relatively large particle sizes are freely filled under the action of an adhesive, spherical graphene particles are more easily contacted with each other, mainly point contact caused by a spherical structure of the spherical or spheroidal graphene microspheres, and layered graphene sheets are prone to surface-to-surface contact with each other, but the contact probability is low, and especially in the preparation process of an actual product, due to the fact that uniform dispersion of graphene filler in an adhesive system is considered, poor contact of single layered graphene sheets is easily caused, or the contact area of contact sites of the spherical graphene particles is too low; however, if the two are compounded, especially if large-particle graphene particles and small-particle layered graphene sheets are compounded, the small-particle layered graphene sheets act as a heat transfer function for adjacent graphene particles under the abutting of spherical graphene particles, so that the contact area between the two is enlarged, a small amount of small-particle graphene sheets can be filled in gaps generated by the spherical particles, and the graphene sheets abutted in the adjacent graphene particles are connected, so that the heat transfer effect is enhanced, and a three-dimensional heat transfer network is formed.
Further, the OI value of the graphene heating film is 45-60;
the OI value is: and (3) adopting XRD diffraction to obtain a diffraction pattern, and then adopting the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 peak in the pattern as the OI value.
By controlling the OI value of the graphene heating film, specifically, controlling the OI value to be 45-60, the orientation of the layered structure of the layered graphene sheets in the graphene heating film can be effectively controlled, so that the layered structure is more prone to be distributed in a disordered state, if the OI value is smaller, the whole graphene sheet layers are more prone to be distributed perpendicular to the substrate, and if the OI value is too large, the graphene sheet layers are more prone to be distributed parallel to the substrate, but in any distribution state, the graphene sheet orientation in the substrate is unified, and the unified distribution state is not beneficial to the matching of effective and spherical graphene particles to form an effective three-dimensional thermal diffusion network.
Further, the quality of the aqueous polyurethane adhesive is as follows: the quality of the graphene sheet is as follows: the mass of the graphene microspheres =8-10:5-7:3-4.
Further, the graphene microspheres are hollow graphene microspheres.
The hollow graphene microsphere has the advantages that more heat is conducted on the wall surface of the hollow graphene microsphere, so that the heat can be conducted between the layered graphene sheet and the spherical graphene microsphere quickly.
Furthermore, dopamine is adsorbed on the surface of the graphene sheet, and at least part of the graphene sheet is adsorbed and fixed on the surface of the graphene microsphere through the dopamine.
A preparation method of a graphene heating film comprises the following specific preparation steps:
ultrasonically dispersing graphene particles and graphene sheets in an aqueous polyurethane solution, uniformly dispersing, and concentrating until the viscosity is 1800-2200 mPa.S to obtain a concentrated solution;
and coating the obtained concentrated solution on the surface of a base membrane, drying, hot-pressing, cooling and rolling to obtain the product.
Further, the drying is as follows: and drying the substance coated on the surface of the base film until the water content is 5-10%.
Further, the hot pressing comprises: rolling at a speed of 150-300mm/min at a temperature of 80-90 deg.C and a pressure of 0.55-0.75 MPa.
And regulating and controlling the orientation of the graphene sheet particles in the substrate in the proper range by regulating reasonable rolling process parameters.
Further, the preparation method of the graphene particles comprises the following steps:
coating dopamine on the surface of spherical alumina microspheres with the particle size distribution of 80-120nm;
then, carrying out ball milling and mixing on the graphene oxide and the spherical alumina microspheres to obtain a ball grinding material;
and reducing the obtained ball milling material, soaking the ball milling material by using acid or alkali liquor to remove an alumina core, and filtering, washing and drying the ball milling material to obtain the graphene particles.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Preparing graphene particles:
dispersing spherical alumina microspheres with the particle size distribution of 80-120nm in dopamine solution with the concentration of 2g/L, stirring and reacting for 2 hours at the rotating speed of 300r/min by using a stirrer, filtering, and collecting filter cakes to obtain spherical alumina microspheres coated with dopamine;
mixing graphene oxide and spherical alumina microspheres according to a mass ratio of 1:1, mixing and pouring into a ball milling tank, and mixing according to a ball material mass ratio of 15:1, adding zirconia ball grinding beads into a ball milling tank, and carrying out ball milling and mixing for 30min to coat graphene oxide on the surface of a spherical alumina microsphere to obtain a ball grinding material;
fully drying the obtained ball grinding material, reducing the ball grinding material by using hydrazine hydrate to reduce graphene oxide, and then carrying out microwave impregnation on the ball grinding material by using a hydrochloric acid solution or a sodium hydroxide solution, wherein the microwave impregnation conditions are controlled as follows: the microwave power is 300W, and the time is 30min; after the impregnation is finished, filtering, collecting a filter cake, washing with deionized water, carrying out vacuum drying on the washed filter cake, and screening out graphene particles with the particle size distribution of 80-120nm;
pretreatment of graphene sheets:
dispersing graphene sheets with the particle size distribution of 20-50nm in a dopamine solution with the concentration of 2g/L, stirring and reacting for 2 hours at the rotating speed of 300r/min by using a stirrer, filtering, and collecting a filter cake to obtain the graphene sheets coated with dopamine, namely the pretreated graphene sheets;
preparation of a product:
according to the mass of the water-based polyurethane adhesive: quality of pretreated graphene sheets: the mass of the graphene microspheres =8:5:3, mixing the three materials, pouring the mixture into a mixer, performing ultrasonic dispersion for 20min under the ultrasonic frequency of 50kHz, and performing reduced pressure concentration under the conditions of pressure of 400Pa and temperature of 65 ℃ until the material viscosity in the mixer reaches 1800mPa & S to obtain a concentrated solution;
transferring the obtained concentrated solution into an extrusion coating machine, controlling the coating thickness to be 50 micrometers, finishing coating on the surface of the base film PET film, and drying the coated material until the water content is 5% to obtain a pre-dried coating film;
and then, carrying out hot pressing on the graphene heating film by using a pair of rollers, rolling at the speed of 150mm/min under the conditions that the temperature is 80 ℃ and the pressure is 0.55MPa to adjust the OI value of the graphene heating film product to be 45, and then sequentially cooling and rolling to obtain the product.
Example 2
Preparing graphene particles:
dispersing spherical alumina microspheres with the particle size distribution of 80-120nm in a dopamine solution with the concentration of 3g/L, stirring and reacting for 3 hours at the rotating speed of 400r/min by using a stirrer, filtering, and collecting filter cakes to obtain spherical alumina microspheres coated with dopamine;
mixing graphene oxide and spherical alumina microspheres according to a mass ratio of 1:1, mixing and pouring into a ball milling tank, and mixing according to a ball material mass ratio of 18:1, adding zirconia ball grinding beads into a ball-milling tank, and carrying out ball-milling mixing for 45min to coat graphene oxide on the surface of a spherical alumina microsphere to obtain a ball grinding material;
fully drying the obtained ball grinding material, reducing the ball grinding material by using hydrazine hydrate to reduce graphene oxide, and then carrying out microwave impregnation on the ball grinding material by using a hydrochloric acid solution or a sodium hydroxide solution, wherein the microwave impregnation conditions are as follows: the microwave power is 320W, and the time is 32min; after the impregnation is finished, filtering, collecting a filter cake, washing with deionized water, carrying out vacuum drying on the washed filter cake, and screening out graphene particles with the particle size distribution of 80-120nm;
pretreatment of graphene sheets:
dispersing graphene sheets with the particle size distribution of 20-50nm in a dopamine solution with the concentration of 3g/L, stirring and reacting for 3 hours at the rotating speed of 400r/min by using a stirrer, filtering, and collecting a filter cake to obtain the graphene sheets coated with dopamine, namely the pretreated graphene sheets;
preparation of a product:
according to the mass of the water-based polyurethane adhesive: quality of pre-treated graphene sheets: the mass of the graphene microspheres =9:6:4, mixing the three materials, pouring the mixture into a mixer, performing ultrasonic dispersion for 30min under the condition that the ultrasonic frequency is 60kHz, and performing reduced pressure concentration under the conditions that the pressure is 450Pa and the temperature is 70 ℃ until the material viscosity in the mixer reaches 2000mPa & S to obtain concentrated solution;
transferring the obtained concentrated solution into an extrusion coating machine, controlling the coating thickness to be 60 mu m so as to finish coating on the surface of the base film PET film, and drying the coated material until the water content is 8% to obtain a pre-dried coating film;
and then, carrying out hot pressing on the graphene thermal film by using a pair of rollers, rolling at the speed of 200mm/min under the conditions that the temperature is 85 ℃ and the pressure is 0.65MPa to adjust the OI value of the graphene thermal film product to be 50, and then sequentially cooling and rolling to obtain the product.
Example 3
Preparing graphene particles:
dispersing spherical alumina microspheres with the particle size distribution of 80-120nm in a dopamine solution with the concentration of 4g/L, stirring and reacting for 4 hours at the rotating speed of 500r/min by using a stirrer, filtering, and collecting filter cakes to obtain spherical alumina microspheres coated with dopamine;
mixing graphene oxide and spherical alumina microspheres according to a mass ratio of 1:1, mixing and pouring the mixture into a ball milling tank, and mixing the mixture according to a ball material mass ratio of 20:1, adding zirconia ball grinding beads into a ball-milling tank, and carrying out ball-milling mixing for 60min to coat graphene oxide on the surface of a spherical alumina microsphere to obtain a ball grinding material;
fully drying the obtained ball grinding material, reducing the ball grinding material by using hydrazine hydrate to reduce graphene oxide, and then carrying out microwave impregnation on the ball grinding material by using a hydrochloric acid solution or a sodium hydroxide solution, wherein the microwave impregnation conditions are as follows: the microwave power is 350W, and the time is 35min; after the impregnation is finished, filtering, collecting a filter cake, washing with deionized water, carrying out vacuum drying on the washed filter cake, and screening out graphene particles with the particle size distribution of 80-120nm;
pretreatment of graphene sheets:
dispersing graphene sheets with the particle size distribution of 20-50nm in a dopamine solution with the concentration of 4g/L, stirring and reacting for 4 hours at the rotating speed of 500r/min by using a stirrer, filtering, and collecting a filter cake to obtain the graphene sheets coated with dopamine, namely the pretreated graphene sheets;
preparation of a product:
according to the mass of the waterborne polyurethane adhesive: quality of pre-treated graphene sheets: the mass of the graphene microspheres =10:7:3, mixing the three materials, pouring the mixture into a mixer, performing ultrasonic dispersion for 40min under the condition that the ultrasonic frequency is 70kHz, and performing reduced pressure concentration under the conditions that the pressure is 500Pa and the temperature is 75 ℃ until the material viscosity in the mixer reaches 2200mPa & S to obtain a concentrated solution;
transferring the obtained concentrated solution into an extrusion coating machine, controlling the coating thickness to be 80 mu m so as to finish coating on the surface of the base film PET film, and drying the coated material until the water content is 10% to obtain a pre-dried coating film;
and then, carrying out hot pressing on the graphene thermal film by using a pair of rollers, rolling at the speed of 300mm/min under the conditions that the temperature is 90 ℃ and the pressure is 0.75MPa to adjust the OI value of the graphene thermal film product to be 60, and then sequentially cooling and rolling to obtain the product.
Example 4
This example differs from example 1 in that: rolling at the speed of 150mm/min under the conditions that the temperature is 75 ℃ and the pressure is 0.48MPa to adjust the OI value of the graphene heating film product to 39; the remaining conditions remained unchanged.
Example 5
This example differs from example 1 in that: rolling at the temperature of 95 ℃ and the pressure of 0.8MPa at the speed of 300mm/min to adjust the OI value of the graphene heating film product to be 66, and keeping the other conditions unchanged.
Example 6
This example differs from example 1 in that: in the graphene sheet pretreatment process, deionized water with equal mass is adopted to replace a dopamine solution, and the rest conditions are kept unchanged.
Comparative example 1
This comparative example is different from example 1 in that: the pretreated graphene sheets with equal mass are adopted to replace the graphene microspheres, and the rest conditions are kept unchanged.
Comparative example 2
This comparative example is different from example 1 in that: the pretreated graphene sheet is replaced by the graphene microsphere with equal mass, and other conditions are kept unchanged.
The products obtained in examples 1-6 and comparative examples 1-2 were tested for their performance, and the specific test methods and test results are as follows:
respectively attaching copper electrodes to the surfaces of the products obtained in the above examples and comparative examples, and then welding conducting wires on the surfaces of the copper electrodes, wherein the samples of the examples and comparative examples for testing are 20cm in length and 10cm in width, and the temperature change in the using process is detected by a temperature polling instrument at the central point and four opposite corners of the sample;
specifically, after a product with a copper electrode adhered is packaged, the product is connected into a direct current power supply, the voltage is adjusted to 10.5V, the power supply is disconnected after the temperature of the central point of the heating film is increased from 25 ℃ to 55 ℃, the temperature is naturally reduced to 25 ℃, the cycle is repeated for 10 times, the time t1 required for the first time from 25 ℃ to 55 ℃ and the time t2 required for the 10 th time from 25 ℃ to 55 ℃ are tested, the time difference of the two times of the central point is calculated to be t1-t2, and the specific test results are shown in the following table 1;
in addition, after the temperature of the first central point is increased to 55 ℃, the temperatures of the other four opposite angles are detected, and the specific test results are shown in table 2;
table 1: product center point performance test results
| Time difference/s | |
| Example 1 | 5.5 |
| Example 2 | 5.2 |
| Example 3 | 5.3 |
| Example 4 | 6.4 |
| Example 5 | 6.6 |
| Example 6 | 6.3 |
| Comparative example 1 | 15.6 |
| Comparative example 2 | 15.8 |
Table 2: temperature test results of different positions of product
| 1# diagonal/deg.C | 2# diagonal/. Degree.C | 3# diagonal/. Degree.C | 4# diagonal/. Degree.C | |
| Example 1 | 54.8 | 54.8 | 54.9 | 54.8 |
| Example 2 | 54.8 | 54.9 | 54.8 | 54.8 |
| Example 3 | 54.9 | 54.8 | 54.8 | 54.9 |
| Example 4 | 54.6 | 54.5 | 54.6 | 54.7 |
| Example 5 | 54.7 | 54.5 | 54.7 | 54.7 |
| Example 6 | 54.6 | 54.5 | 54.7 | 54.5 |
| Comparative example 1 | 52.6 | 52.4 | 52.7 | 52.5 |
| Comparative example 2 | 53.2 | 53.4 | 52.9 | 53.6 |
As can be seen from the test results in Table 1, the product obtained by the invention can obtain relatively uniform heat conduction effect and relatively high heat conduction efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A graphene heating film, comprising: the adhesive comprises a waterborne polyurethane adhesive and graphene dispersed in the polyurethane adhesive;
the graphene comprises two graphene particles with different morphologies;
the graphene particles with different morphologies are respectively a layered graphene sheet and a spherical or spheroidal graphene microsphere;
the particle size distribution of the graphene microspheres is 80-120nm; the particle size distribution of the graphene sheets is 20-50nm;
the mass ratio of the graphene microspheres to the graphene sheets is 3:4-3:7.
2. the graphene exothermic film according to claim 1, wherein the graphene exothermic film has an OI value of 45 to 60;
the OI value is as follows: and (3) diffraction is carried out by adopting XRD, and after a diffraction pattern is obtained, the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 peak in the pattern is taken as the OI value.
3. The graphene heating film according to claim 1, wherein the aqueous polyurethane binder has a mass: the graphene sheet has a mass: the mass of the graphene microspheres =8-10:5-7:3-4.
4. The graphene exothermic film according to claim 1, wherein the graphene microspheres are hollow graphene microspheres.
5. The graphene exothermic film according to claim 1, wherein dopamine is adsorbed on the surface of the graphene sheet, and at least a portion of the graphene sheet is fixed on the surface of the graphene microsphere through the dopamine adsorption.
6. A preparation method of the graphene exothermic film according to any one of claims 1 to 5, characterized by comprising the following specific preparation steps:
ultrasonically dispersing graphene particles and graphene sheets in an aqueous polyurethane solution, uniformly dispersing, and concentrating until the viscosity is 1800-2200mPa & S to obtain a concentrated solution;
and coating the obtained concentrated solution on the surface of a base membrane, drying, carrying out hot pressing, cooling and rolling to obtain the product.
7. The method for preparing the graphene exothermic film according to claim 6, wherein the drying is: and drying the substance coated on the surface of the base film until the water content is 5-10%.
8. The preparation method of the graphene exothermic film according to claim 6, wherein the hot pressing comprises: rolling at a speed of 150-300mm/min at a temperature of 80-90 deg.C and a pressure of 0.55-0.75 MPa.
9. The method for preparing the graphene exothermic film according to claim 6, wherein the step of preparing the graphene particles comprises:
coating dopamine on the surface of spherical alumina microspheres with the particle size distribution of 80-120nm;
then, carrying out ball milling and mixing on the graphene oxide and the spherical alumina microspheres to obtain a ball grinding material;
and reducing the obtained ball milling material, soaking the ball milling material by using acid or alkali liquor to remove an alumina core, and filtering, washing and drying the ball milling material to obtain the graphene particles.
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