CN115522320A - Preparation method of high-modulus polytetrafluoroethylene nanofiber membrane - Google Patents
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Abstract
The invention discloses a preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane, which comprises the following steps: s1, performing ultrasonic dispersion on inorganic nano particles in water, uniformly mixing the inorganic nano particles with mixed emulsion of polytetrafluoroethylene emulsion and polyvinyl alcohol aqueous solution to obtain spinning solution, then preparing a nascent polytetrafluoroethylene nano fiber membrane added with an inorganic nano particle reinforcement by adopting an electrostatic spinning method, and sintering to obtain the polytetrafluoroethylene nano fiber membrane added with the inorganic nano particle reinforcement. The method improves the mechanical strength, self-supporting property, volume stability and other properties of the nanofiber membrane, can flexibly regulate and control the strength and modulus of the nanofiber membrane through the addition of the nanoparticles, is simple and convenient, and is easy for large-scale production.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane.
Background
Polytetrafluoroethylene (PTFE), known as "plastic king," has excellent chemical and thermal stability and can be used for long periods in harsh environments such as strong acid/alkali solutions, corrosive solvents, and the like. The composite filter material is widely applied to the fields of filtering, protective articles, aerospace and the like. The polytetrafluoroethylene membrane has a wide market in the fields of landfill leachate treatment, air filtration, protective clothing, fuel cells and the like.
Because of the insolubility and infusibility of polytetrafluoroethylene, the polytetrafluoroethylene membranes which have been commercialized at present are mainly flat sheet membranes prepared by a biaxial stretching method and hollow fiber membranes prepared by a paste extrusion-stretching method. However, in the fiber-node membrane pore structure, the node difference at the fiber node is large, so that the membrane pore uniformity is poor, the pore size distribution is wide, and the further development of the membrane pore structure is limited.
The electrostatic spinning technology has attracted much attention in recent years due to the characteristics of being capable of preparing nanofiber membranes with uniform structures, narrow pore size distribution and large specific surface areas. Since 2009 there have been more and more reports on the use of electrospinning technology to prepare polytetrafluoroethylene nanofiber membranes and to apply them in the fields of membrane distillation, oil-water separation, waterproof breathable membranes, lithium battery diaphragms, membrane emulsification, etc. However, the polytetrafluoroethylene nanofiber membrane prepared by electrostatic spinning has a small fiber diameter (usually 0.2-1.0 μm), and fiber fracture, membrane shrinkage and even cracking are easy to occur in the sintering process, and the mechanical strength and modulus of the prepared polytetrafluoroethylene nanofiber membrane are poor, so that the requirements of some application fields cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane.
Therefore, the invention adopts the following technical scheme:
a preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane comprises the following steps:
s1, preparing a polytetrafluoroethylene spinning solution added with a reinforcement:
preparing a polyvinyl alcohol aqueous solution with the solid content of 10-15wt%, and standing and defoaming for later use; uniformly dispersing polytetrafluoroethylene emulsion with the solid content of 60wt% in the polyvinyl alcohol aqueous solution under the action of magnetic stirring, stirring for 3 hours to obtain polytetrafluoroethylene/polyvinyl alcohol spinning solution, then dropwise adding boric acid solution with the concentration of 1-5wt%, continuously stirring for 3 hours, and standing for defoaming for 12 hours to obtain mixed emulsion; uniformly dispersing inorganic nano particles in the mixed emulsion to obtain a polytetrafluoroethylene spinning solution added with a reinforcement; wherein:
the ratio of the solid content of the polyvinyl alcohol aqueous solution to the solid content of the polytetrafluoroethylene emulsion is (7-10): 1;
the boric acid accounts for 0.02% of the weight of the polytetrafluoroethylene/polyvinyl alcohol spinning solution;
the solid content ratio of the inorganic nano particles to the polytetrafluoroethylene emulsion is 1 (10-100);
s2, preparing a composite nanofiber primary membrane: spinning the polytetrafluoroethylene spinning solution added with the inorganic nano particle reinforcement obtained in the step 1 by an electrostatic spinning method to obtain an electrostatic spinning polytetrafluoroethylene nano fiber primary membrane added with the inorganic nano particle reinforcement;
and S3, drying the primary membrane obtained in the step 2 to remove the solvent, and sintering in a muffle furnace to obtain the polytetrafluoroethylene nanofiber membrane with high modulus.
Preferably, the inorganic nanoparticles in step S1 are nano-silica, nano-titania, graphene, or carbon nanotubes, and the particle size of the inorganic nanoparticles is 0.01 to 0.5 μm.
The dispersion mode in the step S1 is magnetic stirring, mechanical stirring or ultrasonic dispersion.
Preferably, in step S2, the electrostatic spinning parameters are: the voltage is 25 +/-0.1 kV; the distance between the spinning nozzle and the receiving roller is 12 +/-0.2 cm; the extrusion speed is 0.5ml/h; the inner diameter of the spinning needle head is 0.41mm; the diameter of a rotating cylinder of the electrostatic spinning fiber collector is 10cm, the length of the rotating cylinder is 20cm, and the rotating speed is 350r/min; the receiving substrate is release paper, the spinning time is 2h, and the vacuum drying is carried out for 12h at 60 ℃ after the spinning.
In S3, the temperature rising rate of the primary film during sintering is 1-10 ℃/min, the sintering temperature is 327-400 ℃, and the heat preservation time is 1-4 hours. The optimized heating rate is 1 ℃/min, the sintering temperature is 380 ℃, and the heat preservation time is 3 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention takes the polytetrafluoroethylene nanofiber membrane as a base, improves the mechanical strength, self-supporting property, volume stability and other properties of the nanofiber membrane by adding inorganic nano particles (nano silicon dioxide, nano titanium dioxide, carbon nano tubes, graphene and the like) into polytetrafluoroethylene/polyvinyl alcohol spinning solution through heating, rolling, post-treatment and other modes, provides guarantee for mass production of the polytetrafluoroethylene nanofiber membrane, and further widens the application of the polytetrafluoroethylene nanofiber membrane in the protection fields of waterproof breathable films (protective clothing), waterproof sound-permeable films and the like.
(2) According to the invention, the nano particles can play a role in bonding at the nodes of the polytetrafluoroethylene nano fibers, and the polytetrafluoroethylene nano particles are wrapped by the polytetrafluoroethylene nano particles to form thicker polytetrafluoroethylene nano fibers, so that the strength and the modulus of the polytetrafluoroethylene nano fiber membrane are improved. In the process of adding the reinforcement, the strength of the polytetrafluoroethylene membrane can be regulated and controlled by changing the types of the inorganic nanoparticles, and the strength of the polytetrafluoroethylene nanofiber membrane can be regulated and controlled by changing the content of the inorganic nanoparticles.
(3) The finished membrane is a reinforced polytetrafluoroethylene nanofiber membrane, and has the comprehensive properties of high tensile strength, high modulus, low volume shrinkage and the like on the basis of keeping the strong hydrophobicity, narrow membrane pore size distribution, high and low temperature resistance and high gas flux resistance of the polytetrafluoroethylene nanofiber membrane.
(4) The preparation method has the advantages of wide source of the reinforcement, small influence on the permeability of the membrane, easy operation of the production process and suitability for industrial production.
Drawings
FIG. 1 shows the surface morphology of a reinforcement-free electrospun polytetrafluoroethylene nanofiber nascent membrane prepared in comparative example 1 of the present invention;
FIG. 2 is a surface topography of a sintered reinforcement-free electrospun polytetrafluoroethylene nanofiber membrane prepared in comparative example 1 of the present invention;
FIG. 3 shows the surface morphology of the electrospun polytetrafluoroethylene nanofiber nascent membrane with nano-silica as reinforcement prepared in example 1 of the present invention;
FIG. 4 shows the surface morphology of the electrospun polytetrafluoroethylene nanofiber membrane prepared in example 1 and using nanosilicon dioxide as reinforcement;
FIG. 5 is a drawing curve of the electrospun PTFE nanofiber prepared in example 2 of the present invention and reinforced with titanium dioxide;
FIG. 6 shows the surface morphology of the polytetrafluoroethylene nanofiber membrane with graphene as reinforcement prepared in example 3 of the present invention;
fig. 7 is a digital photo of a teflon nanofiber membrane with graphene as reinforcement prepared in example 3 of the present invention.
Detailed Description
The preparation method of the high modulus polytetrafluoroethylene nanofiber membrane of the invention is described in detail below with reference to the accompanying drawings and examples.
Comparative example 1
A preparation method of a polytetrafluoroethylene nanofiber membrane comprises the following steps:
(1) Preparing a polyvinyl alcohol aqueous solution with solid content of 10wt%, and standing for defoaming for later use; uniformly dispersing polytetrafluoroethylene emulsion with the solid content of 60wt% in the polyvinyl alcohol aqueous solution under the action of magnetic stirring, stirring for 3 hours to obtain polytetrafluoroethylene/polyvinyl alcohol spinning solution, then dropwise adding boric acid solution with the concentration of 5wt%, continuously stirring for 3 hours, and standing for defoaming for 12 hours to obtain mixed emulsion; wherein:
the ratio of the solid content of the polyvinyl alcohol aqueous solution to the solid content of the polytetrafluoroethylene emulsion is 8:1;
the boric acid accounts for 0.02% of the weight of the polytetrafluoroethylene/polyvinyl alcohol spinning solution;
(2) Injecting the polytetrafluoroethylene/polyvinyl alcohol spinning solution into an electrostatic spinning device for electrostatic spinning, wherein the electrostatic spinning parameters are as follows: the voltage is 25kV, the distance between a spinneret and a receiving roller is 12cm, the extrusion speed is 0.5ml/h, the inner diameter of a spinning needle is 0.41mm, the rotating speed of a rotating cylinder (the diameter is 10cm, the length is 20 cm) of an electrostatic spinning fiber collector is 350r/min, and the receiving base material is release paper. After spinning, vacuum drying is carried out for 12h at 60 ℃, and the reinforcement-free electrostatic spinning polytetrafluoroethylene nanofiber nascent membrane is obtained, the surface appearance of which is shown in figure 1, and as can be seen from the figure, polytetrafluoroethylene emulsion particles in polytetrafluoroethylene nanofibers without reinforcement are wrapped by polyvinyl alcohol to form nanofibers with rough surfaces.
(3) And heating the obtained reinforcement-free electrostatic spinning polytetrafluoroethylene nanofiber nascent membrane to 380 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours, and then naturally cooling to obtain the sintered reinforcement-free electrostatic spinning polytetrafluoroethylene nanofiber membrane. The surface appearance is shown in figure 2, and it can be seen from the figure that after sintering, because polyethylene decomposes and polytetrafluoroethylene emulsion particles melt and bond, an obvious particle structure is formed, the bonding between fibers is poor, the fibers have fine diameters and uneven diameter distribution, and stress concentration points are easily formed.
Tested by a universal tester, the tensile strength of the electrostatic spinning polytetrafluoroethylene nanofiber membrane without the reinforcement is 1.1MPa, the elongation at break is 105.5 percent, and the Young modulus is 1.05MPa.
Example 1
A preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane comprises the following steps:
(1) Preparing a polytetrafluoroethylene/polyvinyl alcohol spinning solution in the same manner as in step (1) of comparative example 1;
and (2) ultrasonically dispersing nano silicon dioxide particles (the diameter is 40 nanometers) with the solid content ratio of 1 to 50 of the polytetrafluoroethylene emulsion in distilled water for 2 hours, then adding the mixture into the mixed emulsion, and magnetically stirring for 6 hours to obtain the polytetrafluoroethylene spinning solution taking the nano silicon dioxide as an additive.
(2) Respectively injecting the polytetrafluoroethylene spinning solution prepared in the step (1) into an electrostatic spinning device, and setting electrostatic spinning parameters as follows: the voltage is 25kV, the distance between a spinneret and a receiving roller is 12cm, the extrusion speed is 0.5ml/h, the inner diameter of a spinning needle is 0.41mm, the rotating speed of a rotating cylinder (the diameter is 10cm, the length is 20 cm) of an electrostatic spinning fiber collector is 350r/min, a receiving base material is release paper, and after vacuum drying is carried out for 12h at the temperature of 60 ℃, the electrostatic spinning polytetrafluoroethylene nanofiber primary membrane enhanced by silicon dioxide is obtained, the surface appearance of the electrostatic spinning polytetrafluoroethylene nanofiber primary membrane is shown in figure 3, the nano silicon dioxide can be seen to be agglomerated in the figure, and the structure of beads can be obviously observed on the nanofibers.
(3) And (3) heating the electrostatic spinning polytetrafluoroethylene nanofiber nascent membrane added with the inorganic nano particle reinforcement obtained in the step (2) to 380 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours, and then naturally cooling to obtain the high-modulus polytetrafluoroethylene nanofiber membrane, wherein the surface appearance of the high-modulus polytetrafluoroethylene nanofiber membrane is shown in figure 4.
As can be seen from the figure, due to the introduction of the nano-silica and the agglomeration of the nano-silica, the structure of the nano-fiber is tighter after sintering, the adhesion between fibers is stronger, and the improvement of the strength and the modulus of the nano-fiber film is facilitated.
The tensile strength, elongation at break and Young's modulus of the high modulus polytetrafluoroethylene nanofiber membrane with the nano-silica as the reinforcement are shown in Table 1.
Example 2
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the example 1 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
Example 3
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the example 1 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
Example 4
A preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane comprises the following steps:
(1) Preparing a polytetrafluoroethylene/polyvinyl alcohol spinning solution in the same manner as in step (1) of comparative example 1;
and (2) ultrasonically dispersing nano titanium dioxide particles (P25) with the solid content ratio of 1 to the polytetrafluoroethylene emulsion in distilled water for 2 hours, adding the nano titanium dioxide particles into the mixed emulsion, and magnetically stirring for 6 hours to obtain the polytetrafluoroethylene spinning solution with titanium dioxide nano particles as additives.
(2) Respectively injecting the polytetrafluoroethylene spinning solution prepared in the step (1) into an electrostatic spinning device, and setting electrostatic spinning parameters as follows: the voltage is 25kV, the distance between a spinning nozzle and a receiving roller is 12cm, the extrusion speed is 0.5ml/h, the inner diameter of a spinning needle is 0.41mm, the rotating speed of a rotating cylinder (the diameter is 10cm, the length is 20 cm) of an electrostatic spinning fiber collector is 350r/min, a receiving base material is release paper, and after vacuum drying is carried out for 12h at the temperature of 60 ℃, the electrostatic spinning polytetrafluoroethylene nanofiber primary membrane reinforced by nano titanium dioxide is obtained.
(3) And (3) heating the electrostatic spinning polytetrafluoroethylene nanofiber nascent membrane added with the inorganic nano particle reinforcement obtained in the step (2) to 380 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours, and then naturally cooling to obtain the sintered high-modulus polytetrafluoroethylene nanofiber membrane reinforced by the nano titanium dioxide.
The tensile strength, elongation at break and Young's modulus of the electrostatic spinning polytetrafluoroethylene nanofiber membrane taking the nano titanium dioxide as the reinforcement are shown in Table 1.
Example 5
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the example 4 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
Example 6
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the embodiment 4 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
The tensile curve of the polytetrafluoroethylene nanofiber membranes with titanium dioxide as reinforcement prepared in examples 4-6 is shown in fig. 5, and it can be seen from the figure that the introduction of a proper amount of nano titanium dioxide effectively improves the tensile strength and modulus of the nanofiber membrane, but too much nano titanium dioxide causes stress concentration inside the nanofiber membrane, so that the membrane becomes brittle, the tensile strength is reduced to some extent, and the modulus is higher.
Example 7
A preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane comprises the following steps:
(1) Preparing a polytetrafluoroethylene/polyvinyl alcohol spinning solution, wherein the preparation method of the polytetrafluoroethylene/polyvinyl alcohol spinning solution is the same as that of the step (1) of the comparative example 1;
and (2) ultrasonically dispersing graphene (TA-001A, kaina graphene technology Co., ltd.) with the solid content ratio of 1 to the polytetrafluoroethylene emulsion in distilled water for 2 hours, adding the obtained mixture into the mixed emulsion, and magnetically stirring for 6 hours to obtain the polytetrafluoroethylene spinning solution with the graphene as an additive.
(2) Respectively injecting the polytetrafluoroethylene spinning solution prepared in the step (1) into an electrostatic spinning device, and setting electrostatic spinning parameters as follows: the voltage is 25kV, the distance between a spinning nozzle and a receiving roller is 12cm, the extrusion speed is 0.5ml/h, the inner diameter of a spinning needle is 0.41mm, the rotating speed of a rotating cylinder (the diameter is 10cm, the length is 20 cm) of an electrostatic spinning fiber collector is 350r/min, a receiving base material is release paper, and after vacuum drying is carried out for 12h at the temperature of 60 ℃, the electrostatic spinning polytetrafluoroethylene nanofiber primary membrane enhanced by graphene is obtained.
(3) And (3) heating the electrostatic spinning polytetrafluoroethylene nanofiber primary membrane added with the inorganic nano particle reinforcement obtained in the step (2) to 380 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours, and then naturally cooling to obtain the sintered electrostatic spinning polytetrafluoroethylene nanofiber membrane reinforced by the graphene. The surface morphology is shown in fig. 6, and it can be seen from the figure that the introduction of the conductive graphene and the agglomeration of the graphene make the nanofiber thicker and have higher mechanical strength.
The tensile strength, elongation at break and Young's modulus of the electrostatic spinning polytetrafluoroethylene nanofiber membrane taking graphene as a reinforcement are shown in Table 1.
Example 8
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the example 7 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
Example 9
The preparation method of the high-modulus polytetrafluoroethylene nanofiber membrane is the same as that in the embodiment 7 except that in the step (1), the solid content ratio of the polytetrafluoroethylene emulsion is 1. The digital photo is shown in fig. 7, and it can be seen from the figure that the color of the nanofiber membrane is deepened due to the introduction of the black graphene, and the nanofiber membrane has good self-supporting property.
The tensile strength, elongation at break and Young's modulus of the obtained high-modulus polytetrafluoroethylene nanofiber membrane are shown in Table 1.
TABLE 1 tensile Strength, elongation at Break, young's modulus of samples obtained in comparative examples and examples
| Sample (I) | Tensile Strength (MPa) | Elongation at Break (%) | Young's modulus (MPa) |
| Comparative example 1 | 1.1 | 105.5 | 1.05 |
| Example 1 (1 | 3.5 | 15.2 | 23.1 |
| Example 2 (1 | 3.1 | 16.8 | 18.4 |
| Example 3 (1 | 3.2 | 11.3 | 28.3 |
| Example 4 (1 | 3.3 | 17.8 | 18.5 |
| Example 5 (1 | 2.9 | 13.5 | 21.5 |
| Example 6 (1 | 3.2 | 10.9 | 29.4 |
| Example 7 (1 | 2.5 | 19.2 | 13.0 |
| Example 8 (1 | 3.0 | 15.3 | 19.6 |
| Example 9 (1 | 2.8 | 12.4 | 22.6 |
As can be seen from the data in table 1, the introduction of inorganic nanoparticles (nano-silica, nano-titania or graphene) has a relatively significant effect on both the strength and modulus of the teflon nanofiber membrane, but the inorganic nanoparticles should not be too much to maintain sufficient toughness of the nanofiber membrane and reduce the probability of stress concentration.
Claims (9)
1. A preparation method of a high-modulus polytetrafluoroethylene nanofiber membrane comprises the following steps:
s1, preparing a polytetrafluoroethylene spinning solution added with a reinforcement:
preparing a polyvinyl alcohol aqueous solution with the solid content of 10-15wt%, and standing and defoaming for later use; uniformly dispersing polytetrafluoroethylene emulsion with the solid content of 60wt% in the polyvinyl alcohol aqueous solution under the action of magnetic stirring, stirring for 3 hours to obtain polytetrafluoroethylene/polyvinyl alcohol spinning solution, then dropwise adding boric acid solution with the concentration of 1-5wt%, continuously stirring for 3 hours, and standing for defoaming for 12 hours to obtain mixed emulsion; uniformly dispersing inorganic nano particles in the mixed emulsion to obtain a polytetrafluoroethylene spinning solution added with a reinforcement; wherein:
the ratio of the solid content of the polyvinyl alcohol aqueous solution to the solid content of the polytetrafluoroethylene emulsion is (7-10): 1;
the boric acid accounts for 0.02% of the weight of the polytetrafluoroethylene/polyvinyl alcohol spinning solution;
the solid content ratio of the inorganic nano particles to the polytetrafluoroethylene emulsion is 1 (10-100);
s2, preparing a composite nanofiber primary membrane: spinning the polytetrafluoroethylene spinning solution added with the inorganic nano particle reinforcement obtained in the step 1 by an electrostatic spinning method to obtain an electrostatic spinning polytetrafluoroethylene nano fiber primary membrane added with the inorganic nano particle reinforcement;
and S3, drying the primary membrane obtained in the step 2 to remove the solvent, and sintering in a muffle furnace to obtain the polytetrafluoroethylene nanofiber membrane with high modulus.
2. The method of claim 1, wherein: in S1, the inorganic nanoparticles are ultrasonically dispersed in distilled water for 2 hours and then added into the mixed emulsion.
3. The method of claim 1, wherein: the inorganic nanoparticles in S1 are nano silicon dioxide, nano titanium dioxide, graphene or carbon nanotubes, and the particle size of the inorganic nanoparticles is 0.01-0.5 μm.
4. The method of claim 1, wherein: the dispersing mode in the S1 is magnetic stirring, mechanical stirring or ultrasonic dispersing.
5. The method according to claim 1, wherein in S2, the electrospinning parameters are: the voltage is 25 +/-0.1 kV; the distance between the spinning nozzle and the receiving roller is 12 +/-0.2 cm; the extrusion speed is 0.5ml/h; the inner diameter of the spinning needle head is 0.41mm; the diameter of a rotating cylinder of the electrostatic spinning fiber collector is 10cm, the length of the rotating cylinder is 20cm, and the rotating speed is 350r/min; the receiving substrate is release paper, the spinning time is 2h, and the vacuum drying is carried out for 12h at 60 ℃ after the spinning.
6. The method of claim 1, wherein: in S3, the temperature rising rate of the primary film during sintering is 1-10 ℃/min, the sintering temperature is 327-400 ℃, and the heat preservation time is 1-4 hours.
7. The method of claim 6, wherein: in S3, the temperature rise rate of the primary film during sintering is 1 ℃/min.
8. The method of claim 6, wherein: in step 3, the sintering temperature of the primary film during sintering is 380 ℃.
9. The method of claim 6, wherein: in step 3, the heat preservation time for sintering the primary film is 3 hours.
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