CN111556597A - Method for preparing graphene heating film for battery on surface of polyimide insulating substrate - Google Patents
Method for preparing graphene heating film for battery on surface of polyimide insulating substrate Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004642 Polyimide Substances 0.000 title claims abstract description 58
- 229920001721 polyimide Polymers 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 claims abstract description 87
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000003825 pressing Methods 0.000 claims abstract description 26
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- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
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- 239000010408 film Substances 0.000 claims description 94
- 239000011889 copper foil Substances 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000000853 adhesive Substances 0.000 claims description 18
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- 239000011248 coating agent Substances 0.000 claims description 10
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- 239000002131 composite material Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000011231 conductive filler Substances 0.000 claims description 5
- 239000013039 cover film Substances 0.000 claims description 4
- 238000007646 gravure printing Methods 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229920006332 epoxy adhesive Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001039 wet etching Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 3
- 230000003746 surface roughness Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000000956 alloy Substances 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/615—Heating or keeping warm
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/657—Means for temperature control structurally associated with the cells by electric or electromagnetic means
- H01M10/6571—Resistive heaters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Electromagnetism (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a method for preparing a graphene heating film for a battery on the surface of a polyimide insulating base material, which comprises the following steps: preparing a roughened copper electrode; implanting a roughened copper electrode on the surface of the PI substrate to form a PI-copper electrode substrate structure; printing graphene heating slurry on the surface of a PI-copper electrode base material, baking to form a graphene heating dry film, and enabling the graphene dry film to cover a part of a copper electrode to form a PI-copper electrode-graphene heating layer structure; and pressing and packaging the PI covering film and the PI-copper electrode-graphene heating layer structure: and carrying out local hole opening treatment on the PI covering film, attaching the perforated PI covering film to one side of the PI-copper electrode-graphene heating layer structure, and carrying out hot pressing on the perforated PI covering film and one side of the PI-copper electrode-graphene heating layer structure, wherein the hole opening position of the covering film corresponds to the copper electrode of the PI-copper electrode-graphene heating layer structure, so that a copper electrode terminal is exposed and used for connecting the graphene heating film with an external power supply and a controller.
Description
Technical Field
The invention relates to the technical field of thermal management of power batteries, in particular to a method for manufacturing a flexible heating film of a battery by adopting a graphene material.
Background
In recent years, with the enhancement of global human environmental awareness, the new energy automobile industry has been developed rapidly. In new energy automobiles, the mainstream technology is to adopt a power lithium battery pack as an automobile power source. However, the power lithium battery has a fatal weakness, starting and using are difficult at low temperature, and the low temperature environment seriously affects the service life and the endurance time of the battery. Therefore, the power lithium battery pack must be effectively thermally managed, used in a low-temperature environment, and subjected to a heating treatment.
The traditional products for heating the power battery pack are alloy heating films and modules, and the manufacturing method of the heating products generally adopts a method of wet etching alloy materials to form a heating body, and then the heating body is packaged between two layers of insulating films. The alloy heating film and the module mainly have the following problems: firstly, the alloy heating material has poor far infrared efficiency, the temperature transmission path of the alloy heating material is mainly heat conduction basically, namely the alloy heating material is directly transmitted from the surface of a heating body to the surface of a battery shell, and the heating efficiency is poor; secondly, the heating uniformity of the alloy heating body is poor; finally, the manufacturing process of the alloy heating body has great pollution and great harm to the environment.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
The invention aims to solve one or more of the problems in the prior art, and provides a method for preparing a graphene heating film for a battery on the surface of a polyimide insulating substrate, which comprises the following steps:
preparing a roughened copper electrode;
implanting a roughened copper electrode on the surface of the PI substrate to form a PI-copper electrode substrate structure;
printing graphene heating slurry on the surface of a PI-copper electrode base material, baking to form a graphene heating dry film, and enabling the graphene dry film to cover a part of a copper electrode to form a PI-copper electrode-graphene heating layer structure; and
pressing and packaging the PI covering film and the PI-copper electrode-graphene heating layer structure: and carrying out local hole opening treatment on the PI covering film, attaching the perforated PI covering film to one side of the PI-copper electrode-graphene heating layer structure, and carrying out hot pressing on the perforated PI covering film and one side of the PI-copper electrode-graphene heating layer structure, wherein the hole opening position of the covering film corresponds to the copper electrode of the PI-copper electrode-graphene heating layer structure, so that a copper electrode terminal is exposed and used for connecting the graphene heating film with an external power supply and a controller.
As one aspect of the present invention, the method for preparing the roughened copper electrode comprises:
preparing a rolled copper foil;
putting the rolled copper foil into wet etching equipment, and carrying out microetching on the copper foil by using microetching liquid by adopting a roll-to-roll microetching process; and
and after the copper foil is subjected to microetching, sequentially cleaning and drying the copper foil, and then rolling the copper foil to obtain the roughened copper foil.
Under the action of a strong oxidant, the copper foil generates copper oxide, and then the copper foil reacts with acid to generate an etching effect, wherein the total chemical equation is as follows: H2O2+ Cu + H2SO4 → CuSO4+2H 2O.
As one aspect of the invention, the micro-etching solution is a hydrogen peroxide-sulfuric acid system, the total concentration of hydrogen peroxide and sulfuric acid is 20-150g/L, the concentration ratio of hydrogen peroxide to sulfuric acid is 1: (2.5-3.5).
Preferably, the total concentration of the hydrogen peroxide and the sulfuric acid is 120g/L, wherein the concentration of the hydrogen peroxide is 30g/L, and the concentration of the sulfuric acid is 90 g/L.
In one aspect of the invention, the microetching process is carried out at a reaction temperature of 20 to 35 ℃, preferably 30 ℃.
In one aspect of the invention, the copper foil has a movement speed in the microetching solution of 2 to 4m/min, preferably 3 m/min; the residence time of the copper foil at any position in the microetching solution is 10 to 500s, preferably 100 s.
In one aspect of the invention, the rolled copper foil has a thickness of 12-50 μm, preferably 25 μm; the width of the rolled copper foil is 3-20mm, preferably 10 mm.
In one aspect of the invention, the roughness Ra of the surface of the roughened copper electrode is 1-5 μm; preferably 3 μm.
As one aspect of the present invention, the execution method for implanting the roughened copper electrode on the surface of the PI substrate comprises:
cutting the roughened rolled copper foil to obtain a copper foil strip with the length of 5-30 mm;
coating an acrylic acid adhesive or an epoxy adhesive on the surface of the PI base material, pre-baking at 50-140 ℃ for 1-20min to obtain a PI/semi-cured adhesive composite material, and then pressing and curing the PI/semi-cured adhesive base material and the roughened copper foil strip to form a PI-copper electrode base material, wherein preferably, the curing temperature is 140-; or the like, or, alternatively,
pre-coating a thermoplastic Polyimide (PI) prepolymer (polyamic acid) on the surface of a PI base material, drying to form a semi-cured polyamic acid film to obtain a PI/semi-cured adhesive composite material, preferably, the drying temperature is 120-350 ℃, the drying time is 1-20min, and then carrying out high-temperature lamination on the PI/semi-cured adhesive composite material and the roughened copper foil to finish the imidization process to form a PI-copper electrode base material, preferably, the laminating temperature is 250-350 ℃, and the pressure is 2-10 MPa; or the like, or, alternatively,
and coating polyamic acid on the surface of the roughened copper foil, drying to form a semi-cured polyamic acid film, and performing high-temperature lamination with the PI substrate to finish the imidization process to form the PI-copper electrode substrate, wherein the lamination temperature is preferably 250-350 ℃, and the pressure is 2-10 MPa.
As an aspect of the present invention, the printed graphene is a graphene paste obtained by gravure printing or screen printing of a heat-generating paste. Preferably, the baking temperature is 50-180 ℃, preferably 150 ℃; preferably, the baking time is 1-60min, preferably 20 min.
As one aspect of the present invention, the graphene paste is a mixed system including a graphene conductive filler, a resin adhesive, a solvent, a curing agent, a leveling agent, and a dispersant; further preferably, the graphene conductive filler comprises graphene and/or carbon nanotubes and/or carbon black and/or graphite and/or metal particles.
As one aspect of the invention, the PI cover film and the PI-copper electrode-graphene heating layer structure are laminated and packaged by a rapid pressing method, i.e. the PI-copper electrode-graphene heating layer and the PI cover film are subjected to contraposition compounding and lamination and packaging, the lamination temperature is 140-200 ℃, the lamination time is 10-300s, and the pressure is 50-200kg/cm2. The preferred conditions are: the pressing temperature is 180 ℃, the pressing time is 120s, and the pressure is 150kg/cm2。
In recent years, the graphene heating film is developed rapidly, and the production cost is low and the production process is environment-friendly. Particularly, the graphene heating film can emit far infrared rays, so that surface heating is realized, the heating speed is high, and the graphene heating film becomes a hot spot of competitive research in the field of current heating films. In order to reduce the production cost of the battery heating film, realize low-pollution production and reduce the environmental protection pressure, the original technical idea of adopting an alloy heating body needs to be thoroughly abandoned. Based on the requirements of new energy automobile power lithium battery packs on heating films and the technical defect analysis of the existing alloy heating module, the invention provides a manufacturing method of a battery heating film based on the FPC copper-clad film and printed graphene heating film manufacturing process, which can realize low-cost and large-batch roll production and manufacture, meet the requirements of new energy automobile power lithium battery packs on heating films and improve the comprehensive performance of a battery pack.
According to the invention, by adopting the technical scheme of combining the novel graphene heating film manufacturing and the FPC copper-coated film manufacturing, the printed graphene heating film is used as the heating element of the battery pack heating film to replace the traditional alloy material heating element and pre-implant the copper electrode, and compared with the common heating film technical scheme of post-printing silver paste electrode, the printed graphene heating film has more advantages in the press-fit yield and the electrode weldability. Moreover, the scheme of the invention has the following advantages:
1. the production is more environment-friendly: in the production process, a scheme of etching the alloy electrode in a large area is not needed, only micro-etching liquid is adopted to carry out micro-etching on the copper electrode strip, a small amount of waste liquid is generated, the production process is more environment-friendly, and the cost is low;
2. the process expansibility is good: the heating film can realize roll type automatic production, reduce the production cost and improve the production yield;
3. the performance is better: based on the graphene heating body with high electric-thermal radiation conversion efficiency, the graphene heating module disclosed by the invention has advantages in temperature rise speed and uniformity compared with the traditional alloy heating module (comparative example 1), and the data are shown in table 1.
Drawings
FIG. 1 is a flow chart of a process for preparing a graphene heating film according to the present invention;
FIG. 2 is a cross-sectional view of a graphene heating film according to the present invention;
101-lower layer PI insulating film, 102-upper layer PI insulating film, 201-copper electrode, 301-graphene heating layer prepared by printing, 401-heating film wiring terminal opening region, 501-lower layer PI insulating film surface adhesive layer, 601-upper layer PI insulating film (covering film) surface adhesive layer.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The graphene paste used in the following examples is a mixed system containing a graphene conductive filler, a resin adhesive, a solvent, a curing agent, a leveling agent and a dispersing agent, and is a CCI-305T type graphene far infrared electrothermal paste produced by shenzhen thousand generations of electronic materials, ltd.
Example 1:
the method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate comprises the following process flows of referring to a figure 1:
1) carrying out microetching treatment on the copper electrode material by adopting sulfuric acid-hydrogen peroxide system microetching liquid, wherein the sulfuric acid concentration is 90g/L, the hydrogen peroxide concentration is 30g/L, and the microetching time is 100s, and then cleaning, drying and rolling;
2) coating an acrylic acid adhesive on the surface of the polyimide insulating film, and pre-baking at 80 ℃ for 5min to obtain a PI/semi-cured adhesive composite material;
3) pressing and curing the PI/semi-cured adhesive base material and the roughened copper foil formed in the step 1) at the curing temperature of 180 ℃ for 30min to form a PI-copper electrode base material (see the step A in the figure 1);
4) printing patterned graphene conductive paste (a graphene heating layer) on the surface of the PI-copper electrode base material by adopting a gravure printing method;
5) carrying out thermosetting treatment on the printed graphene slurry under the following treatment conditions: obtaining a PI-copper electrode-graphene heating layer assembly material (see step B in figure 1) at 150 ℃ for 30 min;
6) and (3) pressing the assembly formed in the step (5) with a layer of PI covering film with a local hole, wherein the corresponding hole area on the surface of the PI covering film is overlapped with the copper electrode part area of the assembly formed in the step (5) to form a PI-copper electrode-graphene heating element-PI assembly film (graphene heating film), and exposing the copper electrode part area as a wiring terminal (see step C in the figure 1). The graphene heating film structure is shown in fig. 2.
Example 2:
the method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate comprises the following process flows of referring to a figure 1:
1) carrying out microetching treatment on the copper electrode, adopting sulfuric acid-hydrogen peroxide system microetching liquid, wherein the sulfuric acid concentration is 90g/L, the hydrogen peroxide concentration is 30g/L, and the microetching time is 100s, and then cleaning, drying and rolling;
2) coating an epoxy adhesive on the surface of the polyimide insulating film, and pre-baking at 100 ℃ for 5min to obtain a PI/semi-cured adhesive composite material;
3) pressing and curing the PI/semi-cured adhesive base material and the roughened copper foil formed in the step 1) at the curing temperature of 180 ℃ for 60min to form a PI-copper electrode base material (see the step A in the figure 1);
4) printing patterned graphene conductive paste (a graphene heating layer) on the surface of a PI-copper electrode base material by adopting a screen printing method;
5) carrying out thermosetting treatment on the printed graphene slurry under the following treatment conditions: obtaining a PI-copper electrode-graphene heating layer assembly material (see step B in figure 1) at 150 ℃ for 30 min;
6) and (3) pressing the assembly formed in the step (5) with a layer of PI covering film with a local hole, wherein the corresponding hole area on the surface of the PI covering film is overlapped with the copper electrode part area of the assembly formed in the step (5) to form a PI-copper electrode-graphene heating element-PI assembly film (graphene heating film), and exposing the copper electrode part area as a wiring terminal (see step C in the figure 1). The graphene heating film structure is shown in fig. 2.
Example 3:
the method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate comprises the following process flows of referring to a figure 1:
1) carrying out microetching treatment on the copper electrode, adopting sulfuric acid-hydrogen peroxide system microetching liquid, wherein the sulfuric acid concentration is 90g/L, the hydrogen peroxide concentration is 30g/L, and the microetching time is 100s, and then cleaning, drying and rolling;
2) pre-coating a thermoplastic Polyimide (PI) prepolymer (polyamic acid) on the surface of a PI insulating film, and drying to form a semi-cured polyamic acid film, wherein the drying temperature is 120 ℃ and the drying time is 10 min;
3) and (2) carrying out high-temperature pressing (imidization) on the roughened copper foil formed in the step 1) and the PI/polyamic acid film, wherein the pressing temperature is 280 ℃, the pressure is 5MPa, and the pressing time is 30min, so as to form a PI-copper electrode combined film substrate (see the step A in the figure 1).
4) Printing patterned graphene conductive paste (a graphene heating layer) on the surface of the PI-copper electrode base material by adopting a gravure printing method;
5) carrying out thermosetting treatment on the printed graphene slurry under the following treatment conditions: obtaining a PI-copper electrode-graphene heating layer assembly material (see step B in figure 1) at 150 ℃ for 30 min;
6) and (3) pressing the assembly formed in the step (5) with a layer of PI covering film with a local hole, wherein the corresponding hole area on the surface of the PI covering film is overlapped with the copper electrode part area of the assembly formed in the step (5) to form a PI-copper electrode-graphene heating element-PI assembly film (graphene heating film), and exposing the copper electrode part area as a wiring terminal (see step C in the figure 1). The graphene heating film structure is shown in fig. 2.
Example 4:
the method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate comprises the following process flows of referring to a figure 1:
1) carrying out microetching treatment on the copper electrode, adopting sulfuric acid-hydrogen peroxide system microetching liquid, wherein the sulfuric acid concentration is 90g/L, the hydrogen peroxide concentration is 30g/L, and the microetching time is 100s, and then cleaning, drying and rolling;
2) pre-coating thermoplastic Polyimide (PI) prepolymer (polyamic acid) on the surface (one side) of the copper electrode, and drying to form a semi-cured polyamic acid film, wherein the drying temperature is 120 ℃ and the drying time is 10 min;
3) and (2) performing high-temperature pressing (imidization) on the prepared copper electrode/semi-cured polyamic acid film and PI at the pressing temperature of 280 ℃, the pressing pressure of 5MPa and the pressing time of 30min to form a PI-copper electrode combined film substrate (see step A in figure 1).
4) Printing patterned graphene conductive paste (a graphene heating layer) on the surface of a PI-copper electrode base material by adopting a screen printing method;
5) carrying out thermosetting treatment on the printed graphene slurry under the following treatment conditions: obtaining a PI-copper electrode-graphene heating layer assembly material (see step B in figure 1) at 150 ℃ for 30 min;
6) and (3) pressing the assembly formed in the step (5) with a layer of PI covering film with a local hole, wherein the corresponding hole area on the surface of the PI covering film is overlapped with the copper electrode part area of the assembly formed in the step (5) to form a PI-copper electrode-graphene heating element-PI assembly film (graphene heating film), and exposing the copper electrode part area as a wiring terminal (see step C in the figure 1). The graphene heating film structure is shown in fig. 2.
Comparative example 1:
the comparative example is a power battery heating membrane group (available on the market) adopting alloy and heating materials, and a nickel-chromium-iron alloy resistance circuit is used for replacing graphene in the example 1, and no copper electrode is arranged.
Table 1:
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a graphene heating film for a battery on the surface of a polyimide insulating substrate is characterized by comprising the following steps:
preparing a roughened copper electrode;
implanting a roughened copper electrode on the surface of the PI substrate to form a PI-copper electrode substrate structure;
printing graphene heating slurry on the surface of a PI-copper electrode base material, baking to form a graphene heating dry film, and enabling the graphene dry film to cover a part of a copper electrode to form a PI-copper electrode-graphene heating layer structure; and
pressing and packaging the PI covering film and the PI-copper electrode-graphene heating layer structure: and carrying out local hole opening treatment on the PI covering film, attaching the perforated PI covering film to one side of the PI-copper electrode-graphene heating layer structure, and carrying out hot pressing on the perforated PI covering film and one side of the PI-copper electrode-graphene heating layer structure, wherein the hole opening position of the covering film corresponds to the copper electrode of the PI-copper electrode-graphene heating layer structure, so that a copper electrode terminal is exposed and used for connecting the graphene heating film with an external power supply and a controller.
2. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate according to claim 1, wherein the method for preparing the roughened copper electrode comprises the following steps:
preparing a rolled copper foil;
putting the rolled copper foil into wet etching equipment, and carrying out microetching on the copper foil by using microetching liquid by adopting a roll-to-roll microetching process; and
and after the copper foil is subjected to microetching, sequentially cleaning and drying the copper foil, and then rolling the copper foil to obtain the roughened copper foil.
3. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating base material as claimed in claim 2, wherein the microetching solution is a hydrogen peroxide-sulfuric acid system, the total concentration of hydrogen peroxide and sulfuric acid is 20-150g/L, and the concentration ratio of hydrogen peroxide to sulfuric acid is 1: (2.5-3.5);
preferably, the total concentration of the hydrogen peroxide and the sulfuric acid is 120g/L, wherein the concentration of the hydrogen peroxide is 30g/L, and the concentration of the sulfuric acid is 90 g/L.
4. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulation substrate according to claim 2, wherein in the microetching process, the reaction temperature is 20-35 ℃, and preferably 30 ℃.
5. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulation substrate according to claim 2, wherein the movement speed of the copper foil in the microetching solution is 2-4m/min, preferably 3 m/min; the residence time of the copper foil at any position in the microetching solution is 10 to 500s, preferably 100 s.
6. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulation substrate according to claim 2, wherein the thickness of the rolled copper foil is 12-50 μm, preferably 25 μm; the width of the rolled copper foil is 3-20mm, preferably 10 mm.
7. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate according to claim 1, wherein the coarsened copper electrode has a surface roughness Ra of 1-5 μm; preferably 3 μm.
8. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate according to claim 1, wherein the method for implanting the roughened copper electrode on the surface of the PI substrate is implemented by the following steps:
cutting the roughened rolled copper foil to obtain a copper foil strip with the length of 5-30 mm;
coating an acrylic acid adhesive or an epoxy adhesive on the surface of the PI base material, pre-baking at 50-140 ℃ for 1-20min to obtain a PI/semi-cured adhesive composite material, and then pressing and curing the PI/semi-cured adhesive base material and the roughened copper foil strip to form a PI-copper electrode base material, wherein preferably, the curing temperature is 140-; or the like, or, alternatively,
pre-coating polyamic acid on the surface of a PI base material, drying to form a semi-cured polyamic acid film to obtain a PI/semi-cured adhesive composite material, preferably, the drying temperature is 120-350 ℃, the drying time is 1-20min, and then carrying out high-temperature lamination on the PI/semi-cured adhesive composite material and the roughened copper foil to finish the imidization process to form a PI-copper electrode base material, preferably, the laminating temperature is 250-350 ℃, and the pressure is 2-10 MPa; or the like, or, alternatively,
and coating polyamic acid on the surface of the roughened copper foil, drying to form a semi-cured polyamic acid film, and performing high-temperature lamination with the PI substrate to finish the imidization process to form the PI-copper electrode substrate, wherein the lamination temperature is preferably 250-350 ℃, and the pressure is 2-10 MPa.
9. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate according to claim 1, wherein the printing of the graphene heating paste is performed by gravure printing or screen printing of the graphene paste;
preferably, the baking temperature is 50-180 ℃, preferably 150 ℃;
preferably, the baking time is 1-60min, preferably 20 min;
preferably, the graphene slurry is a mixed system containing a graphene conductive filler, a resin adhesive, a solvent, a curing agent, a leveling agent and a dispersing agent; further preferably, the graphene conductive filler comprises graphene and/or carbon nanotubes and/or carbon black and/or graphite and/or metal particles.
10. The method for preparing the graphene heating film for the battery on the surface of the polyimide insulating substrate according to claim 1, wherein the PI cover film and the PI-copper are coated on the surface of the polyimide insulating substrateThe electrode-graphene heating layer structure is pressed and packaged by a rapid pressing method, i.e. the PI-copper electrode-graphene heating layer and the PI cover film are subjected to contraposition compounding and pressed and packaged, the pressing temperature is 140-200 ℃, the pressing time is 10-300s, and the pressure is 50-200kg/cm2；
The preferred conditions are: the pressing temperature is 180 ℃, the pressing time is 120s, and the pressure is 150kg/cm2。
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Address after: 230000 Parmon Building, No. 16, National E-Commerce Industrial Park, 1201 Huguang East Road, Shushan District, Hefei City, Anhui Province Applicant after: Anhui Aerospace Paimeng Health Technology Co.,Ltd. Address before: 230000 paimeng building, No.16, national e-commerce Industrial Park, 1201 Yuanguang East Road, Shushan District, Hefei City, Anhui Province Applicant before: Anhui Aerospace Paimeng Health Technology Co.,Ltd. |
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Application publication date: 20200818 |