阅读说明：本技术 一种铜电极石墨烯电热膜及其制备方法 (Copper electrode graphene electrothermal film and preparation method thereof ) 是由 刘海滨 于 2020-05-18 设计创作，主要内容包括：本发明公开了一种铜电极石墨烯电热膜,属于电热膜技术领域,所述电热膜由下而上依次为下封装层1、下粘胶层2、石墨烯层3、铜电极层4、上粘胶层5、和上封装层6；各层厚度与弹性模量满足如下关系式：E<Sub>6</Sub>*(D<Sub>5</Sub>+D<Sub>6</Sub>/2)D<Sub>6</Sub>+E<Sub>5</Sub>*D<Sub>5</Sub><Sup>2</Sup>/2＝E<Sub>2</Sub>*D<Sub>2</Sub><Sup>2</Sup>/2+E<Sub>1</Sub>(D<Sub>2</Sub>+D<Sub>1</Sub>/2)D<Sub>1</Sub>；等号两端差异20％以内均认为等式成立。本发明简化了石墨烯电热膜制备工艺,降低了电极材料成本,同时可以通过去除铜电极底部石墨烯或优化各层材料厚度的方法,提升电热膜的耐弯折特性。(The invention discloses a copper electrode graphene electrothermal film, which belongs to the technical field of electrothermal films, wherein the electrothermal film sequentially comprises a lower packaging layer 1, a lower adhesive layer 2, a graphene layer 3, a copper electrode layer 4, an upper adhesive layer 5 and an upper packaging layer 6 from bottom to top; the thickness and the elastic modulus of each layer satisfy the following relational expression: e 6 *(D 5 +D 6 /2)D 6 +E 5 *D 5 2 /2＝E 2 *D 2 2 /2+E 1 (D 2 +D 1 /2)D 1 (ii) a Within 20% difference between the two ends of the equal sign, the equation is considered to be established. The preparation method simplifies the preparation process of the graphene electrothermal film, reduces the cost of electrode materials, and can improve the bending resistance of the electrothermal film by removing graphene at the bottom of the copper electrode or optimizing the thickness of each layer of material.)

1. A copper electrode graphene electrothermal film is characterized in that the electrothermal film sequentially comprises a lower packaging layer (1), a lower adhesive layer (2), a graphene layer (3), a copper electrode layer (4), an upper adhesive layer (5) and an upper packaging layer (6) from bottom to top; the thickness and the elastic modulus of each layer satisfy the following relational expression:

E₆*(D₅+D₆/2)D₆+E₅*D₅ ²/2＝E₂*D₂ ²/2+E₁(D₂+D₁/2)D₁formula (1)

Wherein E is₆、E₅、E₂、E₁The elastic modulus of the materials of the upper packaging layer, the upper adhesive layer, the lower adhesive layer and the lower packaging layer are respectively; d₆、D₅、D₂、D₁The thicknesses of the materials of the upper packaging layer, the upper adhesive layer, the lower adhesive layer and the lower packaging layer are respectively set; within 20% difference between the two ends of the equal sign, the equation is considered to be established.

2. The copper electrode graphene electrothermal film according to claim 1, wherein the copper electrode layer (4) is a copper electrode formed by etching and patterning after a copper foil printing mask is formed.

3. The copper electrode graphene electrothermal film according to claim 1, wherein the thickness of the lower packaging layer (1) is 0.01-0.2 mm; the thickness of the lower adhesive layer (2) is 0.01-0.2mm, the thickness of the graphene layer (3) is 0.33-1nm, the thickness of the copper electrode layer (4) is 0.001-0.1mm, the thickness of the upper adhesive layer (5) is 0.01-0.2mm, and the thickness of the upper packaging layer (6) is 0.01-0.2 mm.

4. The copper electrode graphene electrothermal film according to claim 1, wherein the lower packaging layer (1) is PET, an explosion-proof film or waterproof cloth; the lower adhesive layer (2) is acrylic double-sided adhesive, silica gel double-sided adhesive, EVA hot melt adhesive, TPU hot melt adhesive, PES hot melt adhesive, PO hot melt adhesive or PA hot melt adhesive; the upper adhesive layer (5) is acrylic adhesive sticker or acrylic adhesive sticker; the upper packaging layer (6) is PET, an explosion-proof film or waterproof cloth.

5. A preparation method of the copper electrode graphene electrothermal film as claimed in claim 1, wherein the preparation method comprises the following steps:

(1) sequentially paving a lower adhesive layer (2) and graphene/copper foil on the lower packaging layer (1), and then pressing the lower adhesive layer and the graphene/copper foil together;

(2) manufacturing a copper electrode mask on the surface of the copper foil;

(3) removing the copper foil which is not protected by the mask by using an etching method, and tearing off the mask on the surface of the copper foil to prepare a patterned copper electrode, namely a copper electrode layer (4);

(4) removing graphene on the periphery of the copper electrode frame and part of graphene on the inner side of the frame by laser etching;

(5) cutting an electrode avoiding opening of an upper packaging layer (6) attached with an adhesive layer (5) and then attaching the electrode avoiding opening to a patterned copper electrode in an aligning manner to obtain the copper electrode graphene electrothermal film;

(6) when a plurality of groups of copper electrodes are arranged on each large copper electrode graphene electric heating film once, small pieces need to be cut, and each small piece contains one group of copper electrodes.

6. A preparation method of the copper electrode graphene electrothermal film as claimed in claim 1, wherein the preparation method comprises the following steps:

(1) sequentially paving a lower adhesive layer (2) and graphene/copper foil on the lower packaging layer (1), and then pressing the lower adhesive layer and the graphene/copper foil together;

(2) manufacturing a copper electrode mask on the surface of the copper foil;

(3) removing the copper foil which is not protected by the mask by using an etching method, and tearing off the mask on the surface of the copper foil to prepare a patterned copper electrode, namely a copper electrode layer (4);

(4) cutting an electrode avoiding opening of an upper packaging layer (6) attached with an adhesive layer (5) and then attaching the electrode avoiding opening to a patterned copper electrode in an aligning manner to obtain the copper electrode graphene electrothermal film;

(5) when a plurality of groups of copper electrodes are arranged on each large copper electrode graphene electrothermal film once, small pieces need to be cut, and each small piece contains one group of copper electrodes;

the graphene layer (3) is subjected to patterning treatment, the shape of the graphene layer is overlapped with that of the patterned copper electrode, and the outer edge of the graphene layer (3) is retracted by 0.2-0.3mm compared with that of the patterned copper electrode.

7. The method for preparing the copper electrode mask according to claim 5 or 6, wherein the method for manufacturing the copper electrode mask comprises the following steps: printing or photoetching methods are adopted; the copper foil etching method is characterized in that an ammonium persulfate solution, a hydrochloric acid + hydrogen peroxide solution and a sulfuric acid + hydrogen peroxide solution are adopted for etching; the electrode avoiding opening is processed by a laser cutting or punching method.

Technical Field

The invention relates to the technical field of electrothermal films, in particular to a copper electrode graphene electrothermal film and a manufacturing method thereof.

Background

The graphene electrothermal film has the advantages of good flexibility, stable resistance, transparency, no ignition and the like, the existing graphene electrothermal film mostly adopts silver paste as an electrode, the silver paste is high in cost, the electrothermal film preparation process is complex, the application number is 201510837576.8, and the invention patent named as 'a low-voltage transparent electrothermal film and a preparation process thereof, a high-temperature electrothermal sheet and a preparation process thereof' provides a copper electrode graphene electrothermal film structure and a preparation method thereof, the copper electrode electrothermal film can be prepared by using the method, but the electrothermal film is poor in bending resistance, and the main reasons are two: 1) graphene between the copper electrode and the glue can cause poor adhesion between the copper electrode and the glue; 2) the materials and thickness structures of all layers of the electric heating film are not optimally designed, so that the phenomena of forced peeling of a contact interface between a copper electrode and graphene, graphene fracture and the like can occur during bending.

Disclosure of Invention

In order to solve the problems in the prior art, the applicant of the present invention provides a copper electrode graphene electrothermal film and a manufacturing method thereof. The preparation method simplifies the preparation process of the graphene electrothermal film, reduces the cost of electrode materials, and can improve the bending resistance of the electrothermal film by removing graphene at the bottom of the copper electrode or optimizing the thickness of each layer of material.

The technical scheme of the invention is as follows:

a copper electrode graphene electrothermal film comprises a lower packaging layer 1, a lower adhesive layer 2, a graphene layer 3, a copper electrode layer 4, an upper adhesive layer 5 and an upper packaging layer 6 from bottom to top in sequence; the thickness and the elastic modulus of each layer satisfy the following relational expression:

E₆*(D₅+D₆/2)D₆+E₅*D₅ ²/2＝E₂*D₂ ²/2+E₁(D₂+D₁/2)D₁formula (1)

Wherein E is₆、E₅、E₂、E₁The elastic modulus of the materials of the upper packaging layer, the upper adhesive layer, the lower adhesive layer and the lower packaging layer are respectively; d₆、D₅、D₂、D₁The thicknesses of the materials of the upper packaging layer, the upper adhesive layer, the lower adhesive layer and the lower packaging layer are respectively set; within 20% difference between the two ends of the equal sign, the equation is considered to be established.

The copper electrode layer 4 is a copper electrode formed by etching and patterning after a mask is printed on a copper foil.

The thickness of the lower packaging layer 1 is 0.01-0.2 mm; the thickness of the lower adhesive layer 2 is 0.01-0.2mm, the thickness of the graphene layer 3 is 0.33-1nm, the thickness of the copper electrode layer 4 is 0.001-0.1mm, the thickness of the upper adhesive layer 5 is 0.01-0.2mm, and the thickness of the upper packaging layer 6 is 0.01-0.2 mm.

The lower packaging layer 1 is PET, an explosion-proof film or waterproof cloth; the lower adhesive layer 2 is acrylic double-sided adhesive, silica gel double-sided adhesive, EVA hot melt adhesive, TPU hot melt adhesive, PES hot melt adhesive, PO hot melt adhesive or PA hot melt adhesive; the upper adhesive layer 5 is acrylic adhesive sticker or acrylic adhesive sticker; the upper packaging layer 6 is PET, an explosion-proof film or waterproof cloth.

A preparation method of the copper electrode graphene electrothermal film comprises the following steps:

(1) laying a lower adhesive layer 2 and graphene/copper foil on the lower packaging layer 1 in sequence, and then pressing the lower adhesive layer and the graphene/copper foil together;

(2) manufacturing a copper electrode mask on the surface of the copper foil;

(3) removing the copper foil which is not protected by the mask by using an etching method, and tearing off the mask on the surface of the copper foil to prepare a patterned copper electrode, namely a copper electrode layer 4;

(4) removing graphene on the periphery of the copper electrode frame and part of graphene on the inner side of the frame by laser etching;

(5) cutting an electrode avoiding opening of an upper packaging layer 6 attached with an upper adhesive layer 5, and then aligning and attaching the electrode avoiding opening and a patterned copper electrode to obtain the copper electrode graphene electrothermal film;

(6) when a plurality of groups of copper electrodes are arranged on each large copper electrode graphene electric heating film once, small pieces need to be cut, and each small piece contains one group of copper electrodes.

A preparation method of the copper electrode graphene electrothermal film comprises the following steps:

(1) laying a lower adhesive layer 2 and graphene/copper foil on the lower packaging layer 1 in sequence, and then pressing the lower adhesive layer and the graphene/copper foil together;

(2) manufacturing a copper electrode mask on the surface of the copper foil;

(3) removing the copper foil which is not protected by the mask by using an etching method, and tearing off the mask on the surface of the copper foil to prepare a patterned copper electrode, namely a copper electrode layer 4;

(4) cutting an electrode avoiding opening of an upper packaging layer 6 attached with an upper adhesive layer 5, and then aligning and attaching the electrode avoiding opening and a patterned copper electrode to obtain the copper electrode graphene electrothermal film;

(5) when a plurality of groups of copper electrodes are arranged on each large copper electrode graphene electrothermal film once, small pieces need to be cut, and each small piece contains one group of copper electrodes;

the graphene layer 3 is a patterned graphene layer, the shape of the graphene layer is overlapped with that of the patterned copper electrode, and the outer edge of the graphene layer 3 is retracted by 0.2-0.3mm compared with that of the patterned copper electrode.

The manufacturing method of the copper electrode mask comprises the following steps: printing or photoetching methods are adopted; the copper foil etching method is characterized in that an ammonium persulfate solution, a hydrochloric acid + hydrogen peroxide solution and a sulfuric acid + hydrogen peroxide solution are adopted for etching; the electrode avoiding opening is processed by a laser cutting or punching method.

The beneficial technical effects of the invention are as follows:

compared with the traditional copper electrode graphene electrothermal film, the thickness of each layer of the copper electrode graphene electrothermal film is optimized, so that the copper electrode is positioned at a zero-strain layer position during bending, and the adhesion between the copper electrode and an adhesive layer can be improved by removing part of graphene at the bottom of the copper electrode, so that the bending resistance of the copper electrode graphene electrothermal film is improved.

The copper electrode graphene electrothermal film with the size of 140mm multiplied by 63mm and the resistance of about 4.5 omega designed and manufactured by the invention is bent for 1000 times at the radius of 10mm, the resistance increasing rate is less than 5 percent, and the copper electrode graphene electrothermal film with the same size and resistance manufactured by the conventional method is bent under the same condition, and the resistance increasing rate is more than 50 percent.

Drawings

FIG. 1 is a schematic cross-sectional view of a graphene heating film with copper electrodes according to the present invention;

fig. 2 is a schematic diagram of the graphene/copper foil after being laminated with the lower adhesive layer and the lower packaging layer;

FIG. 3 is a schematic diagram of a copper foil after patterning;

FIG. 4 is a cross-sectional view of a copper foil after patterning;

fig. 5 is a schematic structural diagram after a part of graphene is removed;

fig. 6 is a planar view of the structure with a portion of the graphene removed.

In the figure: 1. a lower encapsulation layer; 2. a lower adhesive layer; 3. a graphene layer; 4. a copper electrode layer; 5. an adhesive layer is arranged; 6. and (7) an upper packaging layer.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings and examples.