Getter film with high initial outbreak rate and lasting moisture absorption rate for perovskite battery and preparation method and application of getter film

Abstract

The invention discloses a getter film with high initial outbreak rate and lasting moisture absorption rate for a perovskite battery and a preparation method and application of the getter film, a support skeleton layer is an expanded polytetrafluoroethylene microporous film layer, and an active layer is a getter active layer formed by infiltrating a getter into a pore structure of the expanded polytetrafluoroethylene microporous film layer. The composite layer is a getter composite layer formed on at least one side surface of the expanded polytetrafluoroethylene microporous membrane layer through a getter. By means of the mode, the periphery of the active material layer of the perovskite cell in a service environment can be kept in a vacuum state for a long time, and it is guaranteed that the perovskite cell is in high photoelectric conversion efficiency and a stable state for a long time; the getter film is coated with a back adhesive layer and is non-corrosive, and the getter film can be directly pasted on a glass cover plate of a perovskite cell or on silver, aluminum and copper electrodes for packaging after the release film is uncovered during use; and the initial explosion rate is high, and moisture and oxygen can be quickly absorbed in the packaging cavity within two hours, so that a vacuum state is achieved.

Description

Technical Field

[0001] The present invention relates to the field of composite films, and in particular to a getter film with high initial burst rate and lasting moisture absorption rate for perovskite cells, and a preparation method and application thereof. Background Art

[0002] At present, broadening the absorption range of light and effectively improving the conversion efficiency of perovskite cells have become the research focus in this field. When perovskite cells are working normally, they are limited by the instability of the structure of hybrid perovskite materials, as well as service environment factors such as humidity and oxygen content, which will accelerate the decomposition of active materials and cause a decrease in photoelectric conversion efficiency, resulting in device performance degradation and affecting the service life of the entire perovskite cell.

[0003] In response to the problem of easy decomposition of active layer materials, researchers are using different hybrid methods to prepare perovskite materials with different structures to increase the stability of photoelectric conversion performance. However, due to the increase in moisture and oxygen content caused by residue, penetration or aging of edge sealant during the service environment of perovskite cells, the perovskite active material layer gradually absorbs moisture and passivates, making it difficult to ensure that the perovskite cell maintains a high photoelectric conversion efficiency and stable state for a long time. In order to effectively prevent problems such as material decomposition, it is very important to control the moisture and oxygen content around the active material layer of the perovskite cell in the service environment. Summary of the invention

[0004] The main technical problem solved by the present invention is to provide a getter film with high initial explosion rate and long-lasting moisture absorption rate for perovskite cells, and a preparation method and application thereof, which overcomes the problem of increased moisture content and oxygen content caused by insufficient vacuum protection in the prior art, can selectively absorb water and oxygen in the service environment of the perovskite cell, has a large absorption capacity for water and oxygen, keeps the active material layer of the perovskite cell in a vacuum state for a long time in the service environment, avoids moisture absorption and passivation of the perovskite active material layer, and ensures that the perovskite cell is in a high photoelectric conversion efficiency and stable state for a long time.

[0005] In order to solve the above technical problems, a technical solution adopted by the present invention is: to provide an absorbent film with high initial explosion rate and long-lasting moisture absorption rate for perovskite batteries, comprising: a supporting skeleton layer, an active layer and a composite layer, the active layer is embedded in the supporting skeleton layer, and the composite layer is connected to at least one side surface of the supporting skeleton layer; the supporting skeleton layer is an expanded polytetrafluoroethylene microporous membrane layer, the active layer is a absorbent active layer formed by embedding the absorbent into the pore structure of the expanded polytetrafluoroethylene microporous membrane layer, the composite layer is a absorbent composite layer formed by the absorbent on at least one side surface of the expanded polytetrafluoroethylene microporous membrane layer, the expanded polytetrafluoroethylene microporous membrane layer, the absorbent active layer and the absorbent composite layer are connected to form an integral absorbent film structure, the absorbent slurry is not only coated on the surface of the expanded polytetrafluoroethylene film, but also embedded in the pore structure of the microporous membrane to form an integral structure, which can improve the film type mechanical strength.

[0006] In a preferred embodiment of the present invention, the thickness of the expanded polytetrafluoroethylene microporous membrane layer is 5 to 300 μm.

[0007] In order to solve the above technical problems, another technical solution adopted by the present invention is: to provide a method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for perovskite battery, comprising the following steps: 1) Prepare expanded polytetrafluoroethylene microporous membrane as a supporting skeleton layer; 2) uniformly mixing the binder, the water absorbent and the oxygen absorbent in a certain proportion to prepare the getter; 3) coating the getter on the surface of the expanded polytetrafluoroethylene microporous membrane layer, and infiltrating it into the pore structure of the expanded polytetrafluoroethylene microporous membrane by thermal curing to form a getter active layer; and firmly covering one side or both sides of the expanded polytetrafluoroethylene microporous membrane to form a getter composite layer; 4) As needed, apply a backing layer on one or both sides of the getter composite layer, and affix a protective release film.

[0008] In a preferred embodiment of the present invention, in step 1), the expanded polytetrafluoroethylene microporous membrane is a single-stretch membrane or a double-stretch membrane with a thickness of 5 to 300 μm.

[0009] In a preferred embodiment of the present invention, in step 2), the binder is polyurethane, polyacrylate or organic silicone resin.

[0010] In a preferred embodiment of the present invention, in step 2), the water absorbent is a mixture of one or more of zeolite, molecular sieve, calcium oxide and calcium chloride, wherein the added content of calcium oxide and calcium chloride is 15wt% to 60wt%.

[0011] In a preferred embodiment of the present invention, in step 2), the oxygen absorbent is a mixture of one or more of iron powder, ferrozirconium alloy FeZr60 and cuprous sulfide, wherein the added content of the iron powder is 0.5wt% to 8wt%.

[0012] In a preferred embodiment of the present invention, in step 3), the getter is coated on the surface of the expanded polytetrafluoroethylene microporous membrane layer using a high-precision surface controllable coating composite technology.

[0013] In order to solve the above technical problems, another technical solution adopted by the present invention is: to provide an application of a getter film with high initial explosion rate and long-lasting moisture absorption rate for perovskite batteries, the getter film including the above-mentioned getter film or the getter film obtained according to the above-mentioned preparation method.

[0014] In a preferred embodiment of the present invention, after the release film of the getter film is peeled off, it is packaged with the cover glass, electrode or substrate of the perovskite cell.

[0015] The beneficial effects of the present invention are as follows: the getter film of the present invention does not require high-temperature activation before use, has excellent weather resistance and temperature resistance, and the use temperature is between -60°C and 120°C; has excellent flexibility and mechanical properties, with a tensile strength of ≥20MPa and an elongation at break of ≥40%; can keep the active material layer of the perovskite battery in a vacuum state for a long time in the service environment, avoid moisture absorption and passivation of the perovskite active material layer, and ensure that the perovskite battery is in a high photoelectric conversion efficiency and stable state for a long time; the thickness and size of the getter film are controllable, and it is covered with a backing layer and is non-corrosive. When in use, the release film is peeled off and can be directly attached to the glass cover of the perovskite battery or to the silver, aluminum, and copper electrodes for packaging. The initial burst rate is high, and the packaging cavity quickly absorbs moisture and oxygen within two hours to reach a vacuum state. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, among which: Figure 1 It is a structural schematic diagram of a preferred embodiment of a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery of the present invention; Figure 2 This is a schematic diagram of a typical packaging structure of a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery of the present invention, which is applied to a perovskite battery; DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0018] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0020] In the description of the present invention, it should be noted that the terms "front", "rear", etc. indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the invention product is usually placed when in use, which is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0021] In the description of the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "disposed" and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be an indirect connection through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0022] In the present invention, unless otherwise clearly specified and limited, a first feature being above or below a second feature may include the first and second features being in direct contact, or may include the first and second features not being in direct contact but being in contact through another feature between them. Moreover, a first feature being above, above, and above a second feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. A first feature being below, below, and below a second feature includes the first feature being directly below and obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.

[0023] See also Figure 1 , the embodiment of the present invention includes: A getter film with high initial explosion rate and sustained moisture absorption rate for perovskite battery, comprising: a supporting skeleton layer 1, an active layer 2 and a composite layer 3, wherein the active layer 2 is embedded in the supporting skeleton layer 1, and the composite layer 3 is connected to at least one side surface of the supporting skeleton layer 1. The composite layer 3 of the present application is composited on both side surfaces of the supporting skeleton layer 1.

[0024] In the present invention, the supporting skeleton layer 1 is an expanded polytetrafluoroethylene microporous membrane layer 1, and the expanded polytetrafluoroethylene microporous membrane is a single-stretch membrane or a double-stretch membrane with a thickness of 5 to 300 μm.

[0025] The active layer 2 is a getter active layer 2 formed by embedding the getter into the pore structure of the expanded polytetrafluoroethylene microporous membrane layer, the composite layer 3 is a getter composite layer 3 formed by the getter on at least one side surface of the expanded polytetrafluoroethylene microporous membrane layer, the expanded polytetrafluoroethylene microporous membrane layer 1, the getter active layer 2 and the getter composite layer 3 are connected to form an integral getter film structure, which overcomes the problem of easy decomposition of the active layer material, improves the mechanical strength of the getter film, has excellent flexibility and mechanical properties, as well as excellent weather resistance and temperature resistance, with a tensile strength of ≥20 MPa and an elongation at break of ≥40%; the use temperature is -60°C ~ 120°C.

[0026] The getter film 6 of the present invention can selectively absorb water and oxygen in the service environment of the perovskite battery, has a large absorption capacity for water and oxygen, keeps the active material layer of the perovskite battery in a vacuum state for a long time in the service environment, avoids moisture absorption and passivation of the perovskite active material layer, and ensures that the perovskite battery is in a high photoelectric conversion efficiency and stable state for a long time.

[0027] The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite cell of the present invention comprises the following steps: 1) Prepare expanded polytetrafluoroethylene microporous membrane as a supporting skeleton layer; 2) The binder, water absorbent and oxygen absorbent are uniformly mixed in a certain proportion to prepare an air absorbent; the binder is polyurethane or polyacrylate or organic silica resin; the water absorbent is a mixture of one or more of zeolite, molecular sieve, calcium oxide and calcium chloride, preferably calcium oxide and calcium chloride, with an added content of 15wt% to 60wt%. The oxygen absorbent is a mixture of one or more of iron powder, zirconium iron alloy FeZr60 and cuprous sulfide, preferably the added content of iron powder is 0.5wt% to 8wt%; 3) The getter is coated on the surface of the expanded polytetrafluoroethylene microporous membrane layer by using high-precision surface controllable coating composite technology, and is embedded into the pore structure of the expanded polytetrafluoroethylene microporous membrane by thermal curing to form a getter active layer 2; and is firmly coated on one or both sides of the expanded polytetrafluoroethylene microporous membrane to form a getter composite layer 3; 4) As required, a backing layer 4 is applied to one or both sides of the getter composite layer 3, and a protective release film 5 is attached thereto.

[0028] The getter film prepared by the preparation method of the present invention has a water vapor absorption capacity of ≥5.5 mg / m2 and an oxygen absorption capacity of ≥6.5 mg / m2 in the first two hours. 2 , and in the later 24 hours, it can absorb the new additions of the day and maintain the water vapor content and oxygen content in the cavity close to 0; wherein, the test conditions are 25°C and 60%RH.

[0029] The getter film of the present invention has controllable thickness and size, is covered with a backing adhesive layer 4, is non-corrosive, and does not require high temperature activation before use. During packaging, after the release film 5 of the getter film 6 is peeled off, it is packaged with the glass cover plate 7 or the silver, aluminum, copper electrode 8 or substrate 9 of the perovskite cell, such as Figure 2 The initial burst rate after encapsulation is high, and the encapsulation cavity quickly absorbs moisture and oxygen within two hours to reach a vacuum state.

[0030] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A getter film with high initial burst rate and long-lasting moisture absorption rate for perovskite battery, characterized in that: include: A support skeleton layer, an active layer and a composite layer, wherein the active layer is embedded in the support skeleton layer, and the composite layer is connected to at least one side surface of the support skeleton layer; the support skeleton layer is an expanded polytetrafluoroethylene microporous membrane layer, the active layer is a getter active layer formed by embedding the getter into the pore structure of the expanded polytetrafluoroethylene microporous membrane layer, the composite layer is a getter composite layer formed by the getter on at least one side surface of the expanded polytetrafluoroethylene microporous membrane layer, and the expanded polytetrafluoroethylene microporous membrane layer, the getter active layer and the getter composite layer are connected to form an overall getter film structure.

2. The getter film with high initial burst rate and long-lasting moisture absorption rate for perovskite battery according to claim 1, characterized in that: The expanded polytetrafluoroethylene microporous membrane layer has a thickness of 5 to 300 μm.

3. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to any one of claims 1-2, characterized in that: The following steps are involved: 1) Prepare expanded polytetrafluoroethylene microporous membrane as a supporting skeleton layer; 2) uniformly mixing the binder, the water absorbent and the oxygen absorbent in a certain proportion to prepare the getter; 3) coating the getter on the surface of the expanded polytetrafluoroethylene microporous membrane layer, and infiltrating it into the pore structure of the expanded polytetrafluoroethylene microporous membrane by thermal curing to form a getter active layer; and firmly covering one side or both sides of the expanded polytetrafluoroethylene microporous membrane to form a getter composite layer; 4) As needed, apply a backing layer on one or both sides of the getter composite layer, and affix a protective release film.

4. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to claim 3, characterized in that: In step 1), the expanded polytetrafluoroethylene microporous membrane is a single-drawn membrane or a double-drawn membrane with a thickness of 5 to 300 μm.

5. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to claim 3, characterized in that: In step 2), the binder is polyurethane, polyacrylate or organic silicone resin.

6. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to claim 3, characterized in that: In step 2), the water absorbent is a mixture of one or more of zeolite, molecular sieve, calcium oxide and calcium chloride, wherein the added content of calcium oxide and calcium chloride is 15wt% to 60wt%.

7. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to claim 3, characterized in that: In step 2), the oxygen absorbent is a mixture of one or more of iron powder, ferrozirconium alloy FeZr60 and cuprous sulfide, wherein the added content of the iron powder is 0.5wt% to 8wt%.

8. The method for preparing a getter film with high initial burst rate and long-lasting moisture absorption rate for a perovskite battery according to claim 3, characterized in that: In step 3), the getter is coated on the surface of the expanded polytetrafluoroethylene microporous membrane layer using a high-precision surface controllable coating composite technology.

9. Application of a getter film with high initial burst rate and long-lasting moisture absorption rate for perovskite battery, characterized in that: The getter film is the getter film according to any one of claims 1 to 2 or the getter film obtained by the preparation method according to any one of claims 3 to 8.

10. The use of the getter film with high initial burst rate and long-lasting moisture absorption rate for perovskite battery according to claim 9, characterized in that: After peeling off the release film of the getter film, it is packaged with the cover glass, electrode or substrate of the perovskite cell.

Images