Perovskite battery assembly containing stacked packaging layer and preparation method thereof

Abstract

The invention belongs to the technical field of perovskite solar cells, and relates to a perovskite cell module containing a stacked packaging layer and a preparation method of the perovskite cell module. The perovskite battery assembly comprises a stacked packaging layer, and the stacked packaging layer is formed by stacking inorganic packaging layers or stacking organic packaging layers and inorganic packaging layers alternately on each other. Wherein the inorganic encapsulation layer has excellent light transmittance and excellent moisture and / or oxygen barrier performance, and the organic encapsulation layer has different components from the inorganic encapsulation layer, so that the performance effect of the inorganic encapsulation layer is supplemented, and the perovskite battery assembly has relatively good mechanical performance; the perovskite solar cell can be effectively protected from being affected by oxygen and moisture, the service life of the cell is prolonged, and the stability of the cell is improved. And the packaging process is simple and low in cost, and can be used for mass production.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cells, and relates to a perovskite battery component containing a stacked encapsulation layer and a preparation method thereof. Background Art

[0002] As a pure renewable energy source, solar energy has advantages that cannot be compared with other energy sources. Since the emergence of photovoltaic power generation, it has quickly become one of the technical means for effectively utilizing solar energy. Perovskite solar cells are a type of photovoltaic device that has rapidly emerged in recent years, and their efficiency has rapidly developed from the initial 3.8% to the current 26.1%. Compared with other mature photovoltaic technologies, the outstanding advantages of perovskite solar cells are low cost, simple preparation, and high photoelectric conversion efficiency, showing potential for commercial development.

[0003] Since the perovskite layer is prone to react with water and oxygen, it particularly easily causes the performance of perovskite solar cells to decay, greatly reducing the service life and application range of perovskite solar cells. Therefore, it is very necessary to encapsulate perovskite solar cells to improve the environmental stability of the devices and block moisture and oxygen in the air. Existing solar cell encapsulation technologies still cannot meet the requirements of practical applications. For example, there are problems such as unreasonable encapsulation structures and poor mechanical properties after encapsulation, and they do not well improve the efficiency stability and service life of the devices, restricting the application scenario range of the devices.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above-mentioned disadvantages of the prior art, and provide a perovskite battery component containing a stacked encapsulation layer and a preparation method thereof to improve the life and stability of the battery.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] This perovskite battery component containing a stacked encapsulation layer includes: a stacked encapsulation layer disposed above the functional layer of the perovskite battery component; the functional layer includes a substrate, a second electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a first electrode layer.

[0008] The stacked encapsulation layer includes an inorganic encapsulation layer; or, the stacked encapsulation layer includes a structure in which an organic encapsulation layer and an inorganic encapsulation layer are alternately stacked on top of each other.

[0009] Wherein, the substrate is transparent glass or transparent plastic such as PET, etc.

[0010] The functional layer includes a substrate, a second electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a first electrode layer stacked in sequence from bottom to top; alternatively, the functional layer includes a substrate, a second electrode layer, an electron transport layer, a perovskite layer, a hole transport layer, and a first electrode layer stacked in sequence from bottom to top;

[0011] The hole transport layer is a layered structure prepared from nickel oxide, doped nickel oxide, cuprous iodide, cuprous thiocyanate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), PEDOT:PSS, or Spiro-OMeTAD, and the thickness of the hole transport layer is 10 - 100 nm;

[0012] The electron transport layer is a layered structure prepared from any one of titanium dioxide (TiO2), tin oxide (SnO2), indium oxide (InO3), zinc oxide (ZnO), PCBM, C 60 or a mixture thereof, and the thickness of the electron transport layer is 10 - 100 nm;

[0013] The material of the second electrode layer is one or more of gold (Au), silver (Ag), copper (Cu), and aluminum (Al). The thickness of the second electrode layer is 10 - 200 nm, and it can be deposited on the substrate through evaporation or PVD process;

[0014] The material of the first electrode layer is one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO). The thickness of the first electrode layer is 10 - 200 nm, and it can be deposited on the electron transport layer or the hole transport layer through magnetron sputtering.

[0015] Further preferably, the stacked encapsulation layer is a multi-layer structure in which an organic encapsulation layer and an inorganic encapsulation layer are alternately stacked on top of each other, and the outermost layer of the stacked encapsulation layer can be an inorganic encapsulation layer.

[0016] Specifically, the thickness of the organic encapsulation layer is 50 nm - 50 μm; the thickness of the inorganic encapsulation layer is 5 nm - 1000 nm;

[0017] The organic encapsulation layer is a polymer film formed by coating an ink composition on the substrate by inkjet printing, spraying, roll coating, knife coating, or spin coating, and then curing by heating or ultraviolet exposure, that is, the organic encapsulation layer.

[0018] Further, the ink composition includes a photocurable monomer and a photoinitiator; the photocurable monomer is any one or a mixture of methacrylate compounds, acrylate compounds, epoxy compounds, vinyl compounds, and vinyl ether compounds.

[0019] Further, the inorganic encapsulation layer can be formed by any one or a combination of chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), sputtering, sublimation, and electron cyclotron resonance plasma-enhanced chemical vapor deposition (ECR-PECVD).

[0020] Further, the inorganic encapsulation layer can include metals or non-metals, oxides of metals or non-metals, nitrides of metals or non-metals, carbides of metals or non-metals, oxynitrides of metals or non-metals, silicides of metals or non-metals, and mixtures thereof.

[0021] Specifically, the inorganic encapsulation layer can include silicon (Si), tin (Sn), antimony (Sb), aluminum (Al), zinc (Zn), antimony (Sb), bismuth (Bi), indium (In), selenium (Se), germanium (Ge), transition metals, and lanthanide metals, but is not limited thereto.

[0022] Preferably, the stacked encapsulation layer is a three-layer structure in which a first inorganic encapsulation layer, an organic encapsulation layer, and a second inorganic encapsulation layer are stacked alternately on top of each other. The first inorganic encapsulation layer and the second inorganic encapsulation layer can respectively include silicon nitride (SiNx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), ZnO, ZnSe, Sb2O3, AlOx, including Al2O3, In2O3, or SnO2. Among them, both x and y are in the range of 1 to 5.

[0023] It should be emphasized that the stacked encapsulation layer is formed by an organic encapsulation layer and an inorganic encapsulation layer; among them, the organic encapsulation layer can flatten the inorganic encapsulation layer and prevent defects in the inorganic encapsulation layer, thereby preventing the penetration of external moisture and oxygen; and, a stacked encapsulation layer can be formed.

[0024] As Figure 1 shown, in the stacked encapsulation layer, a first inorganic encapsulation layer, a first organic encapsulation layer, and a second inorganic encapsulation layer are stacked alternately on top of each other. In other embodiments, the stacked encapsulation layer can be a single-layer inorganic encapsulation layer structure, or the stacked encapsulation layer can be a total of 5 to 7 layers; in a structure where the stacked encapsulation layer contains a total of 5 layers, the stacked encapsulation layer can include a first inorganic encapsulation layer, a first organic encapsulation layer, a second inorganic encapsulation layer, a second organic encapsulation layer, and a third inorganic encapsulation layer stacked in sequence. The inorganic encapsulation layer or the organic encapsulation layer of the stacked encapsulation layer is directly formed on the perovskite solar cell to encapsulate the perovskite solar cell.

[0025] In addition, the present invention also provides a method for preparing a perovskite solar cell module containing a stacked encapsulation layer, and the steps thereof include:

[0026] S1. Pretreat the substrate;

[0027] S2. Sequentially prepare a second electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a first electrode layer on the pretreated substrate;

[0028] S3. Prepare an inorganic encapsulation layer above the first electrode layer by any one or a combination of chemical vapor deposition, plasma-enhanced chemical vapor deposition (such as electron cyclotron resonance plasma-enhanced chemical vapor deposition), sputtering, or sublimation;

[0029] S4. Coating the organic encapsulation layer on the inorganic encapsulation layer by inkjet printing, spraying, roll coating, blade coating, or spin coating, and then forming a polymer film through a curing method such as heating or ultraviolet exposure, which is the organic encapsulation layer;

[0030] S5. Deposit and coat the surface to be encapsulated in the form of alternating inorganic encapsulation layer-organic encapsulation layer-inorganic encapsulation layer, and the inorganic encapsulation layer-organic encapsulation layer-inorganic encapsulation layer finally deposited and coated on the surface of the object to be encapsulated is the stacked encapsulation layer.

[0031] It should be noted that the thickness of the organic encapsulation layer can be adaptively prepared according to actual encapsulation requirements, and the optional thicknesses are 50 nm, 300 nm, 300 nm, 400 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm. The thickness of the inorganic encapsulation layer can also be adaptively prepared according to actual encapsulation requirements, and the optional thicknesses are 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm.

[0032] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0033] The present invention provides a stacked encapsulation layer for encapsulating a perovskite battery, which can be composed of an inorganic encapsulation layer or an organic encapsulation layer and an inorganic encapsulation layer stacked alternately on top of each other. The inorganic encapsulation layer has excellent light transmittance and excellent moisture and / or oxygen barrier properties. The organic layer has a different composition from the inorganic layer, complementing the performance effect of the inorganic layer. This encapsulation structure has good mechanical properties, can effectively protect the perovskite solar cell from oxygen and moisture, and improves the battery life and stability. Moreover, the involved encapsulation process is simple and low-cost, and can be used for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings are incorporated herein and form a part of this specification, and are used together with the specification to explain the principles of the present invention.

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0036] Figure 1 It is a cross-sectional view of a perovskite battery module containing a stacked encapsulation layer provided in Embodiment 1 of the present invention;

[0037] Figure 2 It is a cross-sectional view of a perovskite battery module containing a stacked encapsulation layer provided in Embodiment 5 of the present invention.

[0038] Wherein: 1. Perovskite solar cell; 1-1. First electrode layer; 1-2. Hole transport layer; 1-3. Perovskite layer; 1-4. Electron transport layer; 1-5. Second electrode layer; 1-6. Substrate; 2. Stacked encapsulation layer; 2-1. First inorganic encapsulation layer; 2-2. First organic encapsulation layer; 2-3. Second inorganic encapsulation layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0039] Here, the exemplary embodiments will be described in detail, and the examples are shown in the drawings. When the following description refers to the drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. On the contrary, they are only examples consistent with some aspects of the present invention detailed in the appended claims.

[0040] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below with reference to the drawings and embodiments.

[0041] Embodiment 1

[0042] This embodiment provides a perovskite battery component containing a stacked encapsulation layer, which sequentially includes a substrate 1-6, a second electrode layer 1-5, a hole transport layer 1-2, a perovskite layer 1-3, an electron transport layer 1-4, a first electrode layer 1-1, and a stacked encapsulation layer 2 from bottom to top; see Figure 1 As shown, the stacked encapsulation layer 2 includes a first inorganic encapsulation layer 2-1, a first organic encapsulation layer 2-2, and a second inorganic encapsulation layer 2-3 that are sequentially stacked above the first electrode layer.

[0043] Furthermore, the first inorganic encapsulation layer 2-1 and the second inorganic encapsulation layer 2-3 can both contain inorganic materials with excellent light transmittance, and the first inorganic encapsulation layer 2-1 and the second inorganic encapsulation layer 2-3 can be formed of the same or different inorganic materials; the inorganic encapsulation layer of this embodiment can be silicon nitride (SiNx), where x is in the range of 1 to 5.

[0044] Optionally, the first inorganic encapsulation layer 2-1 and the second inorganic encapsulation layer 2-3 can also be any one or a mixture of SiNx, SiOx, SiOxNy, ZnO, ZnSe, Sb2O3, and AlOx; where x and y are both in the range of 1 to 5.

[0045] Furthermore, the substrate is an ITO transparent conductive substrate; the second electrode layer 1-5 is Ag; the hole transport layer 1-2 is nickel oxide; the electron transport layer 1-4 is TiO2; the first electrode layer 1-1 is ITO, which can be deposited on the electron transport layer 1-4 by magnetron sputtering.

[0046] Furthermore, the organic encapsulation layer is a polymer film formed by coating an ink composition on the substrate by inkjet printing, spraying, roll coating, knife coating, or spin coating, and then curing by heating or ultraviolet exposure. The ink composition includes a curable monomer and a photoinitiator; the photocurable monomer is a methacrylate compound, specifically a mixture of dicyclopentenyloxyethyl methacrylate, 2-phenoxyethyl acrylate, and trimethylolpropane triacrylate; the photoinitiator can be TPO.

[0047] Optionally, the photocurable monomer can also be any one or a mixture of acrylate compounds, epoxy compounds, vinyl compounds, and vinyl ether compounds.

[0048] The preparation method of the above perovskite battery component containing a stacked encapsulation layer includes the following steps:

[0049] S1. Pretreat the substrate 1-6;

[0050] S2. Sequentially prepare a second electrode layer 1-5, a hole transport layer 1-2, a perovskite layer 1-3, an electron transport layer 1-4, and a first electrode layer 1-1 on the pre-treated substrate 1-6;

[0051] S3. Prepare a first inorganic encapsulation layer 2-1 above the first electrode layer 1-1 by chemical vapor deposition;

[0052] S4. Spin-coat a first organic encapsulation layer 2-2 onto the first inorganic encapsulation layer 2-1, and then form a polymer film by ultraviolet exposure curing, which is the first organic encapsulation layer 2-2;

[0053] S5. Then prepare a second inorganic encapsulation layer 2-3 above the first organic encapsulation layer 2-2 by chemical vapor deposition.

[0054] Optionally, the inorganic encapsulation layer is prepared by any one or a combination of chemical vapor deposition, plasma-enhanced chemical vapor deposition, sputtering, or sublimation.

[0055] Furthermore, the thickness of the first inorganic encapsulation layer 2-1 is 50 nm, the thickness of the first organic encapsulation layer 2-2 is 20 μm, and the thickness of the second inorganic encapsulation layer 2-3 is 70 nm.

[0056] Example 2

[0057] Based on Example 1, the difference from Example 1 is that the encapsulation stack layer 2 is an inorganic encapsulation layer with a thickness of 400 nm.

[0058] Example 3

[0059] Based on Example 1, the difference from Example 1 is that the encapsulation stack layer 2 has a five-layer structure, namely a first inorganic encapsulation layer 2-1, a first organic encapsulation layer 2-2, a second inorganic encapsulation layer 2-3, a second organic encapsulation layer, and a third inorganic encapsulation layer; among them, the thicknesses of the first inorganic encapsulation layer 2-1, the second inorganic encapsulation layer 2-3, and the third inorganic encapsulation layer are 60 nm, 80 nm, and 100 nm in sequence, and the thicknesses of the first organic encapsulation layer 2-2 and the second organic encapsulation layer are 10 μm and 15 μm in sequence.

[0060] Example 4

[0061] Based on Example 1, the difference from Example 1 is that the encapsulation stack layer 2 has a 7-layer structure, namely the first inorganic encapsulation layer 2-1, the first organic encapsulation layer 2-2, the second inorganic encapsulation layer 2-3, the second organic encapsulation layer, the third inorganic encapsulation layer, the third organic encapsulation layer, and the fourth inorganic encapsulation layer; among them, the thicknesses of the first inorganic encapsulation layer 2-1, the second inorganic encapsulation layer 2-3, the third inorganic encapsulation layer, and the fourth inorganic encapsulation layer are 10 nm, 20 nm, 90 nm, and 200 nm in sequence, and the thicknesses of the first organic encapsulation layer 2-2, the second organic encapsulation layer, and the third organic encapsulation layer are 7 μm, 12 μm, and 20 μm in sequence.

[0062] Example 5

[0063] Based on Example 1, the difference from Example 1 is that the perovskite solar cell module containing the stacked encapsulation layer includes a substrate 1-6, a second electrode layer 1-5, an electron transport layer 1-4, a perovskite layer 1-3, a hole transport layer 1-2, a first electrode layer 1-1, and a stacked encapsulation layer 2 in sequence from bottom to top, as shown in Figure 2 shown.

[0064] Among them, the stacked encapsulation layer 2 includes a first inorganic encapsulation layer 2-1, a first organic encapsulation layer 2-2, and a second inorganic encapsulation layer 2-3 stacked in sequence above the first electrode layer 1-1; the thickness of the first inorganic encapsulation layer 2-1 is 50 nm, the thickness of the first organic encapsulation layer 2-2 is 30 μm, and the thickness of the second inorganic encapsulation layer 2-3 is 40 nm.

[0065] Comparative example

[0066] The existing Chinese patent document (publication number: CN115084386A, publication date: September 20, 2022) discloses a perovskite solar cell encapsulation structure, which includes a first encapsulation substrate, a perovskite solar cell, and a second encapsulation substrate in sequence from bottom to top; it also includes a pressure component, and the pressure component includes a shell and an elastic component arranged in the shell. The perovskite solar cell is nested in the cavity of the shell, and the elastic component is arranged between the perovskite solar cell and the second encapsulation substrate. The elastic component is arranged circumferentially along the edge of the perovskite solar cell, which is significantly different from the encapsulation structure disclosed in the present invention.

[0067] To verify the effectiveness of the technical solutions provided by the present invention, standard performance tests were carried out on the perovskite solar cell modules disclosed in the above Examples 1 to 5. The specific test methods are as follows:

[0068] (1) Photovoltaic conversion efficiency change test

[0069] Under a standard sunlight test, the photoelectric conversion efficiency of the perovskite solar cells in 5 examples was tracked and tested, and compared with that of the perovskite solar cells in the comparative example at the same time. The results are shown in the following table:

[0070] Table 1: Photoelectric conversion efficiency of perovskite solar cells in Examples 1-5 and comparative example tested at different time points

[0071]

[0072] It should be noted here that each test in each example and comparative example is the average value of the tests of 10 solar cells. From the above test results, it can be seen that compared with the comparative example, the encapsulation structure proposed by the present invention can well maintain the photoelectric conversion efficiency of the solar cell, and at the same time has better oxygen isolation and waterproof performance, thereby improving the life and stability of the battery.

[0073] The above are only specific embodiments of the present invention, enabling those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention.

[0074] It should be understood that the present invention is not limited to the above-described content and can be variously modified and changed without departing from its scope. The scope of the present invention is only limited by the appended claims.

Claims

1. A perovskite battery component containing a stacked encapsulation layer, characterized in that, Comprising: A stacked encapsulation layer (2) disposed on top of the functional layer of the perovskite solar cell module; The stacked encapsulation layer (2) includes an inorganic encapsulation layer; alternatively, the stacked encapsulation layer (2) includes a structure in which an organic encapsulation layer and an inorganic encapsulation layer are alternately stacked on top of each other.

2. The perovskite battery component containing a stacked encapsulation layer according to claim 1, characterized in that, The thickness of the organic encapsulation layer is 50 nm to 50 μm; the thickness of the inorganic encapsulation layer is 5 nm to 1000 nm.

3. The perovskite battery component containing a stacked encapsulation layer according to claim 1, wherein The material of the organic encapsulation layer includes any one or a mixture of methacrylate compounds, acrylate compounds, epoxy compounds, vinyl compounds, and vinyl ether compounds.

4. The perovskite battery component containing a stacked encapsulation layer according to claim 1, characterized in that, The organic encapsulation layer is a polymer film formed by coating an ink composition on a substrate by inkjet printing, spraying, roll coating, knife coating, or spin coating, and then curing by heating or ultraviolet exposure.

5. The perovskite battery component containing a stacked encapsulation layer according to claim 1, characterized in that, The inorganic encapsulation layer includes any one or a mixture of metals or non-metals, oxides of metals or non-metals, nitrides of metals or non-metals, carbides of metals or non-metals, oxynitrides of metals or non-metals, and silicides of metals or non-metals.

6. The perovskite battery component containing a stacked encapsulation layer according to claim 5, characterized in that, The inorganic encapsulation layer includes any one or a mixture of SiNx, SiOx, SiOxNy, ZnO, ZnSe, Sb2O3, and AlOx; wherein, both x and y are in the range of 1 to 5.

7. The perovskite battery component containing a stacked encapsulation layer according to claim 1, wherein, The inorganic encapsulation layer is prepared by any one or a combination of chemical vapor deposition, plasma-enhanced chemical vapor deposition, sputtering, or sublimation.

8. The perovskite battery component containing a stacked encapsulation layer according to claim 1, wherein The material of the first electrode layer (1-1) in the functional layer is one or more of fluorine-doped tin oxide, indium tin oxide, aluminum zinc oxide, gallium zinc oxide, indium zinc oxide, and indium tungsten oxide; the material of the second electrode layer (1-5) in the functional layer is one or more of gold, silver, copper, and aluminum.

9. The perovskite battery component containing a stacked encapsulation layer according to claim 1, characterized in that, The hole transport layer (1-2) in the functional layer is any one or a mixture of nickel oxide, doped nickel oxide, cuprous iodide, cuprous thiocyanate, PTAA, PEDOT:PSS, or Spiro-OMeTAD.

10. The perovskite battery component containing a stacked encapsulation layer according to claim 1, characterized in that, The electron transport layer (1-4) in the functional layer is any one of TiO2, SnO2, InO3, ZnO, PCBM, C 60 or a mixture thereof.

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