Packaging adhesive film and preparation method and application thereof

Abstract

The invention provides a packaging adhesive film and a preparation method and application thereof.The packaging adhesive film comprises a spider silk protein imitating layer, a hydrophobic silicon dioxide aerogel layer and a polyether amine elastomer layer which are arranged in a stacked mode, the three-layer structure is matched, a bionic structure and a dynamic intelligent material are combined, and the packaging adhesive film is obtained. The obtained packaging adhesive film has excellent barrier property and flexibility, also has the advantages of self-repairing property, light weight and low cost, is suitable for being applied to the perovskite battery assembly, and can effectively solve the current three bottlenecks of poor stability, short service life and high environmental risk of the perovskite battery assembly.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesive films, and in particular relates to an encapsulating adhesive film and a preparation method and application thereof. Background Art

[0002] Perovskite solar cells (PSCs) utilize perovskite-type organic metal halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and have attracted widespread attention in recent years due to their high photoelectric conversion efficiency, low mass production costs, and flexible processing capabilities. Because PSC components are highly sensitive to moisture and oxygen, moisture infiltration can cause oxidation of the PSC electrode materials, increasing resistance, reducing device efficiency, and accelerating failure. Therefore, encapsulating PSC components is particularly important.

[0003] At present, traditional battery packaging materials (such as epoxy resin, silicone, etc.) cannot achieve both high barrier properties and excellent flexibility, which will cause perovskite battery components to be prone to lead leakage and interlayer delamination under hot and humid conditions (85℃ / 85%RH), and the lifespan is usually <1000h; in addition, traditional battery packaging materials do not have self-repairing properties. Once damaged during use (such as cracks or breaks), the conversion efficiency of the perovskite battery component will decrease, and even the perovskite battery component will fail and be scrapped directly, seriously affecting its widespread use in perovskite battery components.

[0004] Therefore, developing an encapsulation film with high barrier properties, high flexibility and self-healing properties is still a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide an encapsulation film and its preparation method and application. The encapsulation film has excellent barrier properties and flexibility, and also has the advantages of self-healing, lightweight and low cost, and is very suitable for application in perovskite battery components.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a packaging film, comprising a stacked spider silk protein layer, a hydrophobic silica aerogel layer, and a polyetheramine elastomer layer.

[0008] The encapsulation film provided by the present invention includes a stacked spider silk protein layer, a hydrophobic silica aerogel layer and a polyetheramine elastomer layer; wherein the spider silk protein layer has a β-pleated crystal network, which can not only provide sufficiently high mechanical strength but also has a high elastic modulus; the hydrophobic silica aerogel layer has a lotus leaf-like micro-nano structure, which has both high porosity and excellent hydrophobicity; the polyetheramine elastomer layer has a dynamic imine bond and can self-repair under heating or light; the present invention combines the above three-layer structure by combining the bionic structure with the dynamic intelligent material, so that the obtained encapsulation film has excellent barrier properties and flexibility, and also has the advantages of lightweight, self-repairing and low cost. It is suitable for application in perovskite battery components and can solve the three major bottlenecks currently faced by perovskite battery components: poor stability, short life and high environmental risks.

[0009] Preferably, the thickness of the spider silk protein layer is 5 to 15 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.

[0010] Preferably, the mimic spider silk protein layer is obtained by dissolving recombinant spider silk protein in a solvent and then performing electrostatic spinning.

[0011] Preferably, based on 100 mL of the solvent, the amount of the recombinant spider silk protein is 8 to 12 g, for example, 8 g, 8.5 g, 9 g, 9.5 g, 10 g, 10.5 g, 11 g, 11.5 g or 12 g.

[0012] Preferably, the solvent includes any one of hexafluoroisopropanol, formic acid, trifluoroethanol or hexafluoroacetone, or a combination of at least two thereof.

[0013] Preferably, the voltage of the electrospinning is 10-20 kV, such as 10 kV, 12 kV, 14 kV, 16 kV, 18 kV or 20 kV.

[0014] Preferably, the receiving distance of the electrospinning is 10 to 30 cm, for example, 10 cm, 12 cm, 14 cm, 16 cm, 18 cm, 20 cm, 22 cm, 24 cm, 26 cm, 28 cm or 30 cm.

[0015] Preferably, the thickness of the hydrophobic silica aerogel layer is 30 to 50 μm, for example, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm, 40 μm, 42 μm, 44 μm, 46 μm, 48 μm or 50 μm.

[0016] Preferably, the average pore size of the hydrophobic silica aerogel layer is 20 to 200 nm, for example, 30 nm, 50 nm, 70 nm, 90 nm, 110 nm, 130 nm, 150 nm, 170 nm, 190 nm or 200 nm.

[0017] Preferably, the raw materials of the hydrophobic silica aerogel layer include ethyl orthosilicate, methyltriethoxysilane and 1H,1H,2H,2H-perfluorooctyltriethoxysilane.

[0018] Preferably, the hydrophobic silica aerogel layer is prepared by the following method, which includes: first hydrolyzing ethyl orthosilicate and methyltriethoxysilane, then adding 1H,1H,2H,2H-perfluorooctyltriethoxysilane for dissolution, and drying and forming by supercritical CO2 to obtain the hydrophobic silica aerogel layer.

[0019] Preferably, the molar ratio of ethyl orthosilicate to methyltriethoxysilane is (8-10):1, for example, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, etc.

[0020] Preferably, the hydrolysis reaction is carried out in a mixed solvent of ethanol and hydrochloric acid.

[0021] Preferably, the volume ratio of the ethyl orthosilicate to ethanol is 1:(3-5), for example, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8 or 1:5, etc.

[0022] Preferably, the volume ratio of the ethyl orthosilicate to hydrochloric acid is 1:(0.16-0.2), for example, 1:0.16, 1:0.165, 1:0.17, 1:0.175, 1:0.18, 1:0.185, 1:0.19, 1:0.195 or 1:0.2, etc.

[0023] Preferably, the temperature of the hydrolysis reaction is 50-80°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C.

[0024] Preferably, the hydrolysis reaction time is 150 to 200 min, for example, 150 min, 160 min, 170 min, 180 min, 190 min or 200 min.

[0025] Preferably, based on the total mass of the ethyl orthosilicate and methyltriethoxysilane as 100%, the amount of the 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 0.5-2%, for example, 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7% or 1.9%, etc.

[0026] Preferably, the temperature of the supercritical CO2 drying and molding is 40-50°C, for example, 40°C, 42°C, 44°C, 46°C, 48°C or 50°C.

[0027] Preferably, the pressure of the supercritical CO2 drying molding is 10-15 mPa, such as 10 mPa, 11 mPa, 12 mPa, 13 mPa, 14 mPa or 15 mPa.

[0028] Preferably, the supercritical CO2 drying and molding time is 1 to 3 hours, for example, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3 hours.

[0029] Preferably, the thickness of the polyetheramine elastomer layer is 20 to 30 μm, for example, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm or 30 μm.

[0030] Preferably, the raw materials of the polyetheramine elastomer layer include polyetheramine, glutaraldehyde and a photoinitiator.

[0031] Preferably, the polyetheramine elastomer layer is prepared by the following method, comprising: mixing polyetheramine, glutaraldehyde and a photoinitiator, coating and curing to obtain the polyetheramine elastomer layer.

[0032] Preferably, the molar ratio of the polyetheramine to glutaraldehyde is 1:(0.7-0.9), for example, 1:0.7, 1:0.72, 1:0.74, 1:0.76, 1:0.78, 1:0.8, 1:0.82, 1:0.84, 1:0.86, 1:0.88 or 1:0.9, etc.

[0033] Preferably, based on the total mass of the polyetheramine and glutaraldehyde as 100%, the amount of the photoinitiator is 0.5-3%, for example, 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, 2.1%, 2.3%, 2.5%, 2.7% or 2.9%, etc.

[0034] In the present invention, there is no special requirement for the type of the photoinitiator, and any conventional photoinitiator in the art may be selected, for example, benzophenone or a cationic initiator (such as iodonium salt, etc.) may be selected.

[0035] In the present invention, the coating substrate used for the coating is a PET film.

[0036] Preferably, the curing is ultraviolet curing.

[0037] Preferably, the curing time is 30 to 90 seconds, for example, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, etc.

[0038] In a second aspect, the present invention provides a method for preparing the encapsulating film as described in the first aspect, the preparation method comprising: hot-pressing and compounding a spider silk protein layer, a hydrophobic silica aerogel layer, and a polyetheramine elastomer layer to obtain the encapsulating film.

[0039] Preferably, the temperature of the hot pressing composite is 70-90°C, for example, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C or 90°C.

[0040] Preferably, the hot pressing composite time is 0.5 to 3 min, for example, 0.5 min, 0.7 min, 0.9 min, 1.1 min, 1.3 min, 1.5 min, 1.7 min, 1.9 min, 2.1 min, 2.3 min, 2.5 min, 2.7 min or 2.9 min.

[0041] Preferably, the pressure of the hot pressing composite is 0.2-1 MPa, for example, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa or 1 MPa.

[0042] In a third aspect, the present invention provides a perovskite battery assembly, comprising a first substrate, a perovskite device layer, the encapsulation film as described in the first aspect, and a second substrate that are stacked.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] The encapsulation film provided by the present invention includes a stacked spider silk protein layer, a hydrophobic silica aerogel layer and a polyetheramine elastomer layer. By matching the above three-layer structure, the bionic structure is combined with the dynamic intelligent material, so that the obtained encapsulation film has excellent barrier properties and flexibility, and at the same time has the advantages of self-healing, lightweight and low cost. It is suitable for application in perovskite battery components and can effectively solve the three major bottlenecks currently faced by perovskite battery components: poor stability, short life and high environmental risks. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 A schematic diagram of the cross-sectional structure of the perovskite battery assembly provided by the present invention;

[0046] Among them, 1-first substrate, 2-perovskite device layer, 3-encapsulation film, 3-1-spider silk protein layer, 3-2-hydrophobic silica aerogel layer, 3-3-polyetheramine elastomer layer, 4-second substrate. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0048] Unless otherwise specified, the raw materials involved in the following specific embodiments are all conventional materials in the art and can be obtained by purchasing commercial products.

[0049] Example 1

[0050] A packaging film comprising a stacked spider silk protein layer, a hydrophobic dioxide aerogel layer, and a polyetheramine elastomer layer;

[0051] The thickness of the spider silk protein layer is 10 μm, and the preparation method includes: dissolving 30 g of recombinant spider silk protein (AMSilk, Biosteel) in 300 mL of hexafluoroisopropanol to obtain a spinning solution, and then electrospinning the obtained spinning solution, wherein the electrospinning voltage is 15 kV, the receiving distance is 20 cm, and the flow rate of the spinning solution is 0.8 mL / L, to obtain a spider silk protein layer having a β-pleated crystal network;

[0052] The hydrophobic silica aerogel layer has a thickness of 40 μm and an average pore size of 25 nm. The preparation method comprises: dissolving tetraethyl orthosilicate and methyltriethoxysilane in a molar ratio of 9:1 in a mixed solvent of ethanol and 1 mol / L hydrochloric acid, performing a hydrolysis reaction at 60° C. for 180 min, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 1:4, and the volume ratio of tetraethyl orthosilicate to hydrochloric acid is 1:0.18, then adding 1H,1H,2H,2H-perfluorooctyltriethoxysilane accounting for 1 wt% of the total mass of tetraethyl orthosilicate and methyltriethoxysilane for dissolution, and finally drying and forming the layer by supercritical CO2 at 45° C. and 12 MPa for 2 h to obtain a hydrophobic silica aerogel layer having a lotus leaf-like micro-nanostructure;

[0053] The thickness of the polyetheramine elastomer layer is 25 μm. The preparation method comprises: mixing polyetheramine (Jeffamine, ED-900) and glutaraldehyde at a molar ratio of 1:0.8, adding 0.5 wt% of the total weight of the polyetheramine and glutaraldehyde as a photoinitiator Irgacure 819, coating the mixture on a PET film substrate, and applying the mixture under a wavelength of 365 nm and 10 mW / cm 2 The film was cured under ultraviolet light for 60 seconds and peeled off from the substrate to obtain a polyetheramine elastomer layer containing dynamic imine bonds;

[0054] The preparation method of the encapsulating film provided in this embodiment 1 includes: compounding the spider silk protein layer, the hydrophobic dioxide aerogel layer, and the polyetheramine elastomer layer by hot pressing at 80° C. and 0.5 MPa for 1 min to obtain the encapsulating film.

[0055] Example 2

[0056] A packaging film, which differs from Example 1 only in that the thickness of the spider silk protein layer is 5 μm, and the other structures, materials and preparation methods are the same as those of Example 1.

[0057] Example 3

[0058] A packaging film, which differs from Example 1 only in that the thickness of the spider silk protein layer is 15 μm, and the other structures, materials and preparation methods are the same as those of Example 1.

[0059] Example 4

[0060] A packaging film, which differs from Example 1 only in that the thickness of the hydrophobic silica aerogel layer is 30 μm, and other structures, materials and preparation methods are the same as those of Example 1.

[0061] Example 5

[0062] A packaging film is provided, which differs from Example 1 only in that the thickness of the hydrophobic silica aerogel layer is 50 μm, and the other structures, materials and preparation methods are the same as those of Example 1.

[0063] Example 6

[0064] A packaging film is provided, which differs from Example 1 only in that the thickness of the polyetheramine elastomer layer is 20 μm, and the other structures, materials and preparation methods are the same as those of Example 1.

[0065] Example 7

[0066] A packaging film, which differs from Example 1 only in that the thickness of the polyetheramine elastomer layer is 30 μm, and other structures, materials and preparation methods are the same as those of Example 1.

[0067] Example 8

[0068] A packaging film is provided, which differs from Example 1 only in that the average pore size of the hydrophobic silica aerogel layer is 50 nm. Other structures, materials and preparation methods are the same as those of Example 1.

[0069] Example 9

[0070] A packaging film, which differs from Example 1 only in that the average pore size of the hydrophobic silica aerogel layer is 200 nm. Other structures, materials and preparation methods are the same as those of Example 1.

[0071] Comparative Example 1

[0072] A POE encapsulation film from 3M TM Polyolefin Encapsulant POE 8000.

[0073] Application Example 1

[0074] A perovskite battery component, the cross-sectional structure of which is shown in FIG. Figure 1 As shown, it includes a first substrate 1, a perovskite device layer 2, a packaging film 3 and a second substrate 4 that are stacked;

[0075] The first substrate 1 and the second substrate 4 are both glass substrates, and the thickness is 2.2 mm.

[0076] The perovskite device layer 2 is a multi-layer composite film layer, including a stacked NiOx layer, a SAM layer, a perovskite layer, a passivation layer, a C60 layer, a SnO2 layer and a Cu electrode layer, with a total thickness of 600 nm;

[0077] The packaging film 3 is the packaging film provided in Example 1;

[0078] The preparation method of the perovskite battery assembly provided in this application example 1 includes: laying a perovskite device layer, a packaging film and a second substrate in sequence on a first substrate, laminating and fixing them to obtain the perovskite battery assembly.

[0079] Application Examples 2 to 9

[0080] A perovskite battery assembly differs from Application Example 1 only in that the packaging films provided in Examples 2 to 9 are used to replace the packaging film provided in Example 1, and other structures and materials are the same as those in Application Example 1.

[0081] Comparative Application Example 1

[0082] A perovskite battery assembly differs from Application Example 1 only in that the POE film provided in Comparative Example 1 is used to replace the encapsulation film provided in Example 1, and other structures and materials are the same as those in Application Example 1.

[0083] (1) Performance test of packaging film

[0084] (1) Water and oxygen permeability: Tested in accordance with ISO 15106-1 / 3 (WVTR).

[0085] (2) Elastic modulus: tested according to ASTM D638.

[0086] (3) Self-repair rate: Prepare standard dumbbell-shaped specimens and test the initial tensile strength (σ0) and elongation at break (ε0) (refer to GB / T 1040.1-2018); artificially create penetrating scratches or local perforations, repair them under preset conditions (25°C for 24 h, 50°C for 1 h), and retest the tensile strength (σ1) and elongation at break (ε1) after repair; calculate the repair efficiency = (σ1 / σ0) × 100%.

[0087] The encapsulation films provided in Examples 1 to 9 and Comparative Example 1 were tested according to the above test method. The test results are shown in Table 1:

[0088] Table 1

[0089]

[0090]

[0091] According to the data in Table 1, we can see that:

[0092] The water-oxygen permeability of the encapsulation films provided in Examples 1 to 9 is only 3.11×10 -7 ~3.38×10 -7 g / day·m 2, an elastic modulus of up to 157-200 MPa, a self-healing efficiency of 40-60%, and excellent barrier properties, flexibility and self-healing properties; while the conventional commercially available POE encapsulation film provided in Comparative Example 1 has a high water and oxygen permeability, a low elastic modulus, and has no self-healing properties at all.

[0093] (2) Performance test of perovskite battery components

[0094] (1) Device efficiency: tested under standard test conditions (STC).

[0095] (2) Damp-heat (85°C / 85%RH) aging: The device efficiency is tested after 2000h of damp-heat aging test at 85°C / 85%RH according to IEC 61215-2:2016 standard.

[0096] The perovskite battery components provided in Examples 1 to 9 and Comparative Application Example 1 were tested according to the above test method. The test results are shown in Table 2:

[0097] Table 2

[0098]

[0099]

[0100] According to the data in Table 2, we can see that:

[0101] The device efficiency of the perovskite battery components provided in Application Examples 1 to 9 is as high as 14.87-15.15%, and the device efficiency after the damp heat aging test is still as high as 14.65-14.91%, and the stability is very strong; in contrast, the perovskite battery component provided in Application Example 1 not only has a lower device efficiency, but also has a lower device efficiency after the damp heat aging test, indicating that the stability is very poor.

[0102] The applicant states that while the present invention uses the aforementioned embodiments to illustrate an encapsulating film, its preparation method, and its application, the present invention is not limited to the aforementioned process steps, nor does it necessarily rely on the aforementioned process steps for implementation. Persons skilled in the art should understand that any improvements to the present invention, equivalent substitutions for selected raw materials, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A packaging film, characterized in that: The packaging film comprises a spider silk protein layer, a hydrophobic silica aerogel layer and a polyetheramine elastomer layer which are stacked.

2. The packaging film according to claim 1, wherein The thickness of the spider silk protein layer is 5 to 15 μm.

3. The packaging film according to claim 1, wherein: The spider silk protein-like layer is obtained by dissolving recombinant spider silk protein in a solvent and then performing electrostatic spinning.

4. The encapsulating film according to any one of claims 1 to 3, characterized in that: The thickness of the hydrophobic silica aerogel layer is 30 to 50 μm; And / or, the average pore size of the hydrophobic silica aerogel layer is 20 to 200 nm.

5. The packaging film according to claim 4, characterized in that The hydrophobic silica aerogel layer is prepared by the following method, which includes: first hydrolyzing ethyl orthosilicate and methyltriethoxysilane, then adding 1H,1H,2H,2H-perfluorooctyltriethoxysilane for dissolution, and drying and forming through supercritical CO2 to obtain the hydrophobic silica aerogel layer.

6. The encapsulating film according to any one of claims 1 to 3, characterized in that: The thickness of the polyetheramine elastomer layer is 20 to 30 μm.

7. The packaging film according to claim 6, wherein: The polyetheramine elastomer layer is prepared by the following method, which includes: mixing polyetheramine, glutaraldehyde and a photoinitiator, coating and curing to obtain the polyetheramine elastomer layer.

8. A method for preparing the encapsulating film according to any one of claims 1 to 7, characterized in that: The preparation method comprises: hot-pressing and compounding a spider silk imitation protein layer, a hydrophobic silica aerogel layer and a polyetheramine elastomer layer to obtain the packaging film.

9. The preparation method according to claim 8, characterized in that The temperature of the hot pressing compound is 70-90°C and the time is 0.5-3 minutes; And / or, the pressure of the hot pressing composite is 0.2-1 MPa.

10. A perovskite battery assembly, characterized in that: The perovskite battery assembly includes a first substrate, a perovskite device layer, the packaging film according to any one of claims 1 to 7, and a second substrate that are stacked.

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