阅读说明：本技术 太阳能电池模块 (Solar cell module ) 是由 山本辉明 根上卓之 于 2019-11-13 设计创作，主要内容包括：本发明提供一种可具有高耐久性的太阳能电池模块。本发明的太阳能电池模块(100)具备：第一基板(1)、设在与第一基板(1)相对置的位置上的第二基板(2)、在第一基板(1)上且设在第一基板(1)与第二基板(2)之间的太阳能电池(3)、充满第一基板(1)与第二基板(2)之间的空间的填充材料(4)及设在太阳能电池(3)的表面中的面向第二基板(2)的主表面(3a)上的保护层(5)。太阳能电池(3)具有层叠结构,其包含含有钙钛矿型化合物的光电转换层(6)、空穴传输层(7)及电子传输层(8)。保护层(5)含有聚酰亚胺。保护层(5)由被覆太阳能电池(3)的主表面(3a)的第一区域(9)和使主表面(3a)露出的第二区域(10)构成。保护层(5)中离散地配置有第一区域(9)或第二区域(10)。(The invention provides a solar cell module which can have high durability. A solar cell module (100) is provided with: the solar cell module includes a first substrate (1), a second substrate (2) provided at a position opposed to the first substrate (1), a solar cell (3) provided on the first substrate (1) and between the first substrate (1) and the second substrate (2), a filler (4) filling a space between the first substrate (1) and the second substrate (2), and a protective layer (5) provided on a main surface (3a) of a surface of the solar cell (3) facing the second substrate (2). The solar cell (3) has a layered structure and includes a photoelectric conversion layer (6) containing a perovskite-type compound, a hole transport layer (7), and an electron transport layer (8). The protective layer (5) contains polyimide. The protective layer (5) is composed of a first region (9) that covers the main surface (3a) of the solar cell (3) and a second region (10) that exposes the main surface (3 a). The protective layer (5) is provided with first regions (9) or second regions (10) in a discrete manner.)

1. A solar cell module is provided with:

a first substrate,

A second substrate provided at a position facing the first substrate,

A solar cell disposed on the first substrate and between the first substrate and the second substrate,

A filling material filling a space between the first substrate and the second substrate, and

a protective layer provided on a main surface facing the second substrate among surfaces of the solar cell;

here, the solar cell has a laminated structure including a photoelectric conversion layer containing a perovskite-type compound, a hole transport layer, and an electron transport layer,

the protective layer contains a polyimide which is a polyimide,

the protective layer is composed of a first region covering the main surface of the solar cell and a second region exposing the main surface, and is formed of

In the protective layer, the first region or the second region is discretely arranged.

2. The solar cell module according to claim 1, wherein the second region in the protective layer is a plurality of openings that penetrate in a thickness direction of the protective layer and are discretely arranged.

3. The solar cell module according to claim 1 or 2, wherein the first region is discretely arranged in the protective layer.

4. The solar cell module according to any one of claims 1 to 3, wherein an area ratio of the second region in the protective layer is 7% or more and 60% or less.

5. The solar cell module according to any one of claims 1 to 4, wherein an effective area ratio of the second region in the protective layer is 24% or more and 91% or less.

6. The solar cell module of any one of claims 1-5, wherein the first substrate is transparent.

7. The solar cell module according to any one of claims 1 to 6, wherein the electron transport layer contains titanium oxide.

8. The solar cell module according to any one of claims 1 to 7, wherein the hole transport layer contains polytriallylamine.

9. The solar cell module according to any one of claims 1 to 8, wherein the photoelectric conversion layer contains CH₃NH₃PbI₃。

Technical Field

The present invention relates to a solar cell module.

Background

In recent years, research and development of perovskite-type solar cells are being carried out. Perovskite type solar cell will use composition formula ABX₃(here, a is a 1-valent cation, B is a 2-valent cation, and X is a 1-valent anion) or a crystal structure similar thereto (hereinafter referred to as "perovskite-type compound") is used as a light absorbing material. In the present specification, a solar cell using a perovskite-type compound is referred to as a "perovskite-type solar cell".

Non-patent document 1 discloses a basic structure of a perovskite-type solar cell. A perovskite-type solar cell having a basic structure includes a transparent electrode, an electron transport layer, a light absorption layer (hereinafter referred to as "perovskite layer") using perovskite-type crystals for light absorption and photoelectric charge separation, a hole transport layer, and a collector electrode in this order. That is, the electron transport layer (n), the perovskite layer (i), and the hole transport layer (p) are stacked in this order from the transparent electrode side. Such a configuration is referred to as an n-i-p structure or a forward stacked structure.

Non-patent document 2 discloses a perovskite-type solar cell having a structure in which a hole transport layer, a perovskite layer, and an electron transport layer are stacked in this order from the transparent electrode side. Such a configuration is referred to as a p-i-n structure or an inverted stacked structure.

A solar cell is a device that generates electricity by receiving sunlight, that is, a device that uses sunlight as an energy source. Therefore, the solar cell is generally installed outdoors for use. Therefore, in order for the solar cell to withstand outdoor environments such as high temperatures and weather, a sealing structure called a solar cell module is required.

Documents of the prior art

Non-patent document

Non-patent document 1: julian Burchcka et al 6 names, "Nature" (UK), 7 months 2013, volume 499, p.316-319

Non-patent document 2: wei Chen et al 10, "SCIENCE" (USA), 11 months 2015, 350 th volume, No. 6263, p.944-948

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a solar cell module having high durability.

Means for solving the problems

The present invention relates to a solar cell module, including:

a first substrate,

A second substrate provided at a position facing the first substrate,

A solar cell disposed on the first substrate and between the first substrate and the second substrate,

A filling material filling a space between the first substrate and the second substrate, and

a protective layer provided on a main surface facing the second substrate among surfaces of the solar cell;

here, the solar cell has a laminated structure including a photoelectric conversion layer containing a perovskite-type compound, a hole transport layer, and an electron transport layer,

the protective layer contains a polyimide which is a polyimide,

the protective layer is composed of a first region covering the main surface of the solar cell and a second region exposing the main surface, and is formed of

In the protective layer, the first region or the second region is discretely arranged.

Effects of the invention

The invention provides a solar cell module with high durability.

Drawings

Fig. 1A is a cross-sectional view schematically showing a solar cell module according to an embodiment of the present invention.

Fig. 1B is a sectional view of the protective layer in a plane on the I-I chain line of the solar cell module shown in fig. 1A.

Fig. 2A is a cross-sectional view schematically showing a modification of the solar cell module according to the embodiment of the present invention.

Fig. 2B is a sectional view of the protective layer in a plane on the II-II chain line of the solar cell module shown in fig. 2A.

Fig. 3 is a cross-sectional view schematically showing a solar cell module of a first comparative embodiment.

Fig. 4A is a cross-sectional view schematically showing a solar cell module according to a second comparative embodiment.

Fig. 4B is a sectional view of the protective layer in a plane on the III-III chain line of the solar cell module shown in fig. 4A.

Fig. 5A is a cross-sectional view schematically showing a solar cell module of a third comparative embodiment.

Fig. 5B is a sectional view of the protective layer in a plane on the IV-IV chain line of the solar cell module shown in fig. 5A.

FIG. 6 is a graph (graph) showing the relationship between the area ratio of the second region and the maintenance ratio of the Fill Factor (FF).

Fig. 7 is a graph showing a relationship between the area ratio of the second region and the maintenance ratio of the open circuit voltage (Voc).

Fig. 8 is a graph showing a relationship between the area ratio of the second region and the maintenance ratio of the open circuit voltage (Voc).

Fig. 9 is a graph showing a relationship between the area ratio of the second region and the maintenance ratio of the open circuit voltage (Voc).

Fig. 10 is a graph showing a relationship between the area ratio of the second region and the maintenance ratio of the open circuit voltage (Voc).

Fig. 11 is a graph showing a relationship between the effective area ratio in the second region and the maintenance ratio of the open circuit voltage (Voc).

Fig. 12 is a graph showing a relationship between the effective area ratio in the second region and the maintenance ratio of the open circuit voltage (Voc).

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

Fig. 1A is a cross-sectional view schematically showing a solar cell module 100 according to the present embodiment. Fig. 1B is a sectional view of the protective layer in a plane on the I-I chain line of the solar cell module 100 shown in fig. 1A.

As shown in fig. 1A, the solar cell module 100 includes a first substrate 1, a second substrate 2, a solar cell 3, a filler 4, and a protective layer 5. The second substrate 2 is provided at a position opposed to the first substrate 1. The solar cell 3 is on the first substrate 1 and is disposed between the first substrate 1 and the second substrate 2. The filling material 4 fills the space between the first substrate 1 and the second substrate 2. The protective layer 5 is provided on the main surface 3a facing the second substrate 2 among the surfaces of the solar cells 3.

The solar cell 3 has a laminated structure including a photoelectric conversion layer 6 containing a perovskite-type compound, a hole transport layer 7, and an electron transport layer 8. For example, in the solar cell 3, the electron transport layer 8, the photoelectric conversion layer 6, and the hole transport layer 7 are stacked in this order. The solar cell 3 may further contain other layers. For example, a porous layer may be provided between the electron transport layer 8 and the photoelectric conversion layer 6. Although not shown in fig. 1, the solar cell 3 further includes an electrode as an output terminal. That is, the solar cell 3 may have a laminated structure in which a first electrode (not shown), an electron transport layer 8, a photoelectric conversion layer 6, a hole transport layer 7, and a second electrode (not shown) are laminated in this order.

The protective layer 5 includes a first region 9 covering the main surface 3a of the solar cell 3 and a second region 10 exposing the main surface 3 a. The protective layer 5 contains polyimide. That is, the first region 9 of the protective layer 5 is composed of a material containing polyimide.

In the example shown in fig. 1A and 1B, the second regions 10 are discretely arranged in the protective layer 5. In this case, in the protective layer 5, the second regions 10 are a plurality of openings that penetrate in the thickness direction of the protective layer 5 and are discretely arranged. More specifically, in this case, the protective layer 5 is composed of, for example, a film containing polyimide. As shown in fig. 1A, the thin film has a plurality of openings that penetrate in the thickness direction and are discretely arranged as the second region 10. The shape of the opening is not particularly limited, and may be a circular shape as shown in fig. 1B, a polygonal shape, or the like. The plurality of openings may be arranged at substantially constant intervals on the main surface 3a of the solar cell 3.

Next, basic operational effects of the respective configurations of the solar cell module 100 of the present embodiment will be described.

When light is irradiated to the solar cell 3, the photoelectric conversion layer 6 absorbs the light, and excited electrons and holes are generated. The excited electrons move to the electron transport layer 8. On the other hand, holes generated in the photoelectric conversion layer 6 move to the hole transport layer 7. Current can be taken out by using the first electrode connected to the electron transport layer 8 as a negative electrode and the second electrode connected to the hole transport layer 7 as a positive electrode.

In the solar cell module 100, a space between the first substrate 1 and the second substrate 2 is filled with the filler 4. By providing the filler 4, the mechanical strength of the solar cell module 100 can be improved and the displacement of the internal components can be suppressed.

By providing the protective layer 5 on the main surface 3a of the solar cell 3, peeling at the interface between the photoelectric conversion layer 6 and the hole transport layer 7 or at the interface between the photoelectric conversion layer 6 and the electron transport layer 8 can be suppressed. The effects of this operation will be described in more detail. In the case of integrating the whole by filling the space between the first substrate 1 and the second substrate 2 with the filler 4, for example, a heat crimping method can be generally employed. In this case, first, a laminate in which the filler 4 is disposed between the first substrate 1 on which the solar cell 3 is provided and the second substrate 2 disposed to face the first substrate 1 is produced. Next, the material of the filler 4 is melted by heating, and the entire laminate is pressure-bonded, whereby the first substrate 1, the solar cell 3, the filler 4, and the second substrate 2 are integrated. In the case of the configuration in which the entire main surface 3a of the solar cell 3 is in contact with the filler 4, when the filler 4 is heated and melted to press bond the laminate, peeling may occur at the interface where the bonding force between the layers is weak in the solar cell 3 due to, for example, flow drag of the filler 4. This interfacial delamination is likely to occur at the interface between the photoelectric conversion layer 6 and the hole transport layer 7 or at the interface between the photoelectric conversion layer 6 and the electron transport layer 8. In the solar cell module 100 of the present embodiment, the protective layer 5 is provided between the main surface 3a of the solar cell 3 and the filler 4. Since the protective layer 5 contains polyimide, it has excellent heat resistance and excellent rubbing resistance. Therefore, even when the laminate is pressed in a state where the material of the filler 4 is melted by heating, the protective layer 5 is interposed between the main surface 3a of the solar cell 3 and the filler 4. As a result, interlayer peeling of the solar cell 3 due to flow drag of the filler 4 or the like can be suppressed.

The protective layer 5 is provided with second regions 10 that are discretely arranged to expose the main surface 3a of the solar cell 3. The second region 10 can suppress a decrease in solar cell characteristics due to the desorption gas staying at a high concentration on the surface of the solar cell 3. The desorption gas is a desorption gas from a material constituting the protective layer 5, that is, a polyimide-containing material constituting the first region 9. The desorption gas diffuses, for example, into the entire packing material 4.

As described above, the protective layer 5 can simultaneously suppress interfacial peeling between layers of the multilayer structure constituting the solar cell 3 and suppress degradation due to the desorbed gas.

The protective layer 5 is not limited to the structure shown in fig. 1A and 1B. Fig. 2A is a cross-sectional view schematically showing a solar cell module 200 which is a modification of the solar cell module of the present embodiment. Fig. 2B is a sectional view of the protective layer in a plane on the II-II chain line of the solar cell module 200 shown in fig. 2A. The protective layer may be a protective layer 11 composed of first regions 12 and second regions 13 which are discretely arranged as shown in fig. 2A and 2B. The first region 12 may be composed of a plurality of films containing polyimide. The shape of the discretely arranged thin films is not particularly limited, and may be a strip shape as shown in fig. 2B, a polygonal shape, or the like. A plurality of thin films may be disposed on the main surface 3a of the solar cell 3 at substantially constant intervals.

With reference to the solar cell module of the comparative system, a difference in effects due to the arrangement and formation of the first regions 9 and 12 and the second regions 10 and 13 in the protective layers 5 and 11 will be described. Fig. 3 is a cross-sectional view schematically showing a solar cell module 300 according to a first comparative embodiment. Fig. 4A is a cross-sectional view schematically showing a solar cell module 400 according to a second comparative embodiment. Fig. 4B is a sectional view of the protective layer in a plane on the III-III chain line of the solar cell module 400 shown in fig. 4A. Fig. 5A is a cross-sectional view schematically showing a solar cell module 500 according to a third comparative embodiment. Fig. 5B is a sectional view of the protective layer in a plane on the IV-IV chain line of the solar cell module 500 shown in fig. 5A.

The solar cell module 300 shown in fig. 3 has a structure in which the solar cell and the filler are in contact with each other without a protective layer on the main surface of the solar cell. The first substrate 101, the second substrate 102, the solar cell 103, the filler 104, the photoelectric conversion layer 106, the hole transport layer 107, and the electron transport layer 108 shown in fig. 3 correspond to the first substrate 1, the second substrate 2, the solar cell 3, the filler 4, the photoelectric conversion layer 6, the hole transport layer 7, and the electron transport layer 8 of the solar cell modules 100 and 200, respectively. Therefore, a detailed description thereof will be omitted. The same applies to fig. 4 and 5 below. In the structure of the solar cell module 300, peeling may occur at the interface between the photoelectric conversion layer 106 and the hole transport layer 107 or the electron transport layer 108. When such peeling occurs, the diode characteristics in the solar cell 103 are degraded. Therefore, the occurrence of such peeling becomes a factor of lowering the rectification property.

The solar cell module 400 shown in fig. 4A and 4B has a protective layer 109 different from the solar cell module 100 shown in fig. 1A and 1B and the solar cell module 200 shown in fig. 2A and 2B. The protective layer 109 of the solar cell module 400 does not include the second region but is constituted only by the first region. That is, the solar cell module 400 has a configuration in which the protective layer 109 completely covers the entire main surface, which is the power generation region of the solar cell 103. In the case of this configuration, desorption gas from the material of the protective layer 109 is accumulated at a high concentration on the surface of the solar cell 103. Such gas stagnation is a factor of deterioration in the solar cell characteristics.

The solar cell module 500 shown in fig. 5A and 5B has a protective layer 110 different from the solar cell module 100 shown in fig. 1A and 1B and the solar cell module 200 shown in fig. 2A and 2B. The protective layer 110 of the solar cell module 500 has a first region 111 and a second region 112. However, in the protective layer 110, both the first region 111 and the second region 112 are not discretely arranged. That is, the first area 111 and the second area 112 are each formed as a continuous area that is pieced together. In this case, as shown in fig. 5A and 5B, in the power generation region of the solar cell 103, that is, in the region where the first region 111 completely covers the main surface, the desorbed gas from the material of the first region 111 constituting the protective layer 110 remains at a high concentration on the surface of the solar cell 103. Such gas stagnation is a factor of deterioration in the solar cell characteristics.

In the solar cell modules 100 and 200 of the present embodiment, the protective layer provided on the main surface of the solar cell facing the second substrate is configured by a first region covering the main surface of the solar cell and a second region exposing the main surface, and the first region or the second region is discretely arranged. With this configuration, the solar cell modules 100 and 200 can achieve both the effect of suppressing the interfacial separation in the first region and the effect of suppressing the degradation of the desorption gas in the second region.

The solar cell modules 100 and 200 of the present embodiment can be manufactured by the following method, for example.

First, a first electrode is formed on the surface of the first substrate 1. Next, the electron transit layer 8 is formed on the first electrode of the first substrate 1 by a sputtering method or the like. Next, the photoelectric conversion layer 6 is formed on the electron transport layer 8 by a coating method or the like. Next, the hole transport layer 7 is formed on the photoelectric conversion layer 6 by a coating method or the like. Next, a second electrode is formed on the hole transport layer 7 by vapor deposition or the like.

Through the above steps, the solar cell 3 can be formed on the first substrate 1.

Next, protective layers 5 and 11 are formed on the solar cell 3. In forming the protective layer such as the protective layer 5 in which the second regions are discretely arranged, for example, a film containing polyimide is first prepared, and a plurality of openings are formed so as to penetrate through the film in the thickness direction and are discretely arranged. By disposing this thin film on the solar cell 3, the protective layer 5 can be formed. In forming a protective layer such as the protective layer 11 in which the second regions are discretely arranged, for example, a plurality of polyimide-containing films having a predetermined shape (for example, a belt shape) are prepared. The protective layer 11 can be formed by disposing the thin film on the solar cell 3 so as to form a predetermined pattern.

Next, the first substrate 1, the second substrate 2 provided at a position facing the first substrate 1, and the filler 4 disposed between the first substrate 1 and the second substrate 2 are integrated by integral molding using heat press bonding or the like. This makes it possible to obtain the solar cell modules 100 and 200.

The respective configurations of the solar cell modules 100 and 200 will be described in detail below.

[ first substrate 1]

The first substrate 1 is disposed on the light-receiving surface side of the solar cell modules 100 and 200. The first substrate 1 has, for example, water vapor barrier properties and light transmittance. The first substrate 1 may also be transparent. In addition, the first substrate 1 physically serves to hold each layer constituting the solar cell 3 as a film when manufacturing the solar cell modules 100 and 200. Examples of the first substrate 1 include a glass substrate and a plastic substrate. The plastic substrate may be a plastic film.

[ second substrate 2]

The second substrate 2 is provided at a position facing the first substrate 1 of the solar cell module 100 or 200. The second substrate 2 has, for example, water vapor barrier properties. The second substrate 2 in turn also serves to protect the solar cell 3. The second substrate 2 can suppress physical damage of the solar cell 3 due to external factors such as sand, for example. Examples of the second substrate 2 are a glass substrate or a plastic substrate. The plastic substrate may be a plastic film. The second substrate 2 does not necessarily need to be light transmissive. Therefore, an Al deposited thin film or the like can be used as the second substrate 2.

[ photoelectric conversion layer 6]

The photoelectric conversion layer 6 contains, for example, ABX as a light absorbing material₃The compound having a perovskite structure is described. A is a monovalent cation. Examples of A include monovalent cations such as alkali metal cations and organic cations. More specifically, examples of A include methylammonium Cation (CH)₃NH₃ ⁺) Formamidinium cation (NH)₂CHNH₂ ⁺) Cesium cation (Cs)⁺) Or rubidium cation (Rb)⁺). B is a cation having a valence of 2. B is, for example, a transition metal or a 2-valent cation of a group 13 to group 15 element. More specifically, an example of B is Pb²⁺、Ge²⁺Or Sn²⁺. X is a 1-valent anion such as a halogen anion. A. The site of each of B or X may be occupied by a plurality of ions. A specific example of a compound having a perovskite structure is CH₃NH₃PbI₃、CH₃CH₂NH₃PbI₃、NH₂CHNH₂PbI₃、CH₃NH₃PbBr₃、CH₃NH₃PbCl₃、CsPbI₃、CsPbBr₃、RbPbI₃Or RbPbBr₃And the like. The photoelectric conversion layer 6 may be of the composition formula ABX₃The perovskite-type compound is a structure similar to the compound having a perovskite structure. Examples of the similar structure include a structure containing a defect of a halogen anion in the perovskite compound, and a structure in which a 1-valent cation or a halogen anion in the perovskite compound is composed of a plurality of elements.

The thickness of the photoelectric conversion layer 6 is, for example, 100nm or more and 1000nm or less. The thickness of the photoelectric conversion layer 6 may depend on the magnitude of light absorption of the photoelectric conversion layer 6. The photoelectric conversion layer 6 can be formed by a coating method using a solution, a co-evaporation method, or the like. The photoelectric conversion layer 6 may be partially mixed with the electron transport layer 8.

[ hole transport layer 7]

The hole transport layer 7 is made of, for example, an organic semiconductor or an inorganic semiconductor. The hole transport layer 7 may have a structure in which layers made of the same constituent material are stacked, or may have a structure in which layers made of different materials are alternately stacked. Examples of the organic semiconductor include Polytriallylamine (PTAA), 2',7,7' -tetrakis [ N, N-bis (p-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), or poly-3, 4-ethylenedioxythiophene (PEDOT). Examples of the inorganic semiconductor include a p-type inorganic semiconductor. Examples of the p-type inorganic semiconductor include CuO and Cu₂O, CuSCN, molybdenum oxide, or nickel oxide.

[ Electron transport layer 8]

The electron transport layer 8 contains a semiconductor. The electron transport layer 8 may be a semiconductor having a band gap of 3.0eV or more. By forming the electron transport layer 8 with a semiconductor having a band gap of 3.0eV or more, visible light and infrared light can be transmitted to the light absorbing layer 6. Examples of the semiconductor include an organic n-type semiconductor and an inorganic n-type semiconductor.

Examples of organic n-type semiconductors are imide compounds, quinone compounds, fullerenes or fullerene derivatives. Examples of the inorganic n-type semiconductor include metal oxides and perovskite-type oxides. Examples of the metal oxide include oxides of Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si or Cr. Specific examples thereof include titanium oxide (i.e., TiO)₂). Examples of perovskite type oxides are SrTiO₃Or CaTiO₃。

[ Filler 4]

As the filler 4, a known filler for a solar cell module can be used. Examples of the filler material 4 are Ethylene Vinyl Acetate (EVA) or Polyolefin (PO).

[ protective layers 5, 11]

As described above, the protective layers 5 and 11 have the first regions 9 and 12 covering the main surface 3a of the solar cell 3 and the second regions 10 and 13 exposing the main surface 3a of the solar cell 3. The material of the protective layers 5, 11, i.e. the material of the first regions 9, 12, contains polyimide. Polyimide has insulating properties and is excellent in flexibility, heat resistance and chemical resistance. The first regions 9 and 12 formed of such a material can reduce the propagation of stress to the interface between the layers in the solar cell 3 due to the displacement of the filler 4. Therefore, the first regions 9 and 12 can suppress interfacial peeling in the solar cell 3.

The second regions 10 and 13 of the protective layers 5 and 11 expose the main surface 3a of the solar cell 3. In other words, the second regions 10 and 13 are regions of the protective layers 5 and 11 that do not cover the main surface 3a of the solar cell 3. That is, the second regions 10 and 13 function to partially expose the main surface 3a without completely covering the entire main surface 3a with the first regions 9 and 12. Therefore, the second regions 10 and 13 can suppress the degradation of the solar cell characteristics caused by the desorption gas from the material of the first regions 9 and 12 staying at a high concentration on the surface of the solar cell 3. The second region can achieve the above-described effects regardless of the configuration of the second region 10 formed by the opening provided in the film and the second region 13 provided as a region other than the discretely arranged first regions.

The area ratio of the second regions 10 and 13 in the protective layers 5 and 11 may be 7% to 60%, for example. When the area ratio of the second region is 7% or more, the retention of the desorbed gas from the first regions 9 and 12 can be sufficiently suppressed. When the area ratio of the second region is 60% or less, the interfacial peeling in the solar cell 3 can be sufficiently suppressed, and sufficient mechanical strength of the protective layers 5 and 11 can be ensured.

The effective area ratio of the second regions 10 and 13 in the protective layers 5 and 11 may be, for example, 24% or more and 91% or less. When the effective area ratio of the second region is 24% or more, the retention of the desorption gas from the first regions 9 and 12 can be sufficiently suppressed. When the effective area ratio of the second region is 91% or less, the interface peeling in the solar cell 3 can be sufficiently suppressed, and the good mechanical strength of the protective layers 5 and 11 can be ensured. Here, the effective area of the second region will be described. The second region of the protective layer may be formed of a plurality of openings which are discretely arranged, or may be formed of a region other than the first region which is discretely arranged. In any case, it is considered necessary to make the distance from the position of the desorption gas to the second region equal to or shorter than a predetermined distance in order to discharge the desorption gas from the second region. The certain distance is the effective distance over which the desorption gas can be evacuated. The effective distance may be, for example, 0.2 mm. For example, when the second region is an opening, it is considered that gas located at a distance equal to or less than the effective distance from the edge of the opening can be discharged from the opening. Therefore, the area of the second region is calculated by expanding according to the effective distance, and the obtained area is defined as the effective area of the second region. For example, when the opening has a circular shape and the effective distance is 0.2mm, the effective area of the opening is calculated by using "the diameter of the opening +0.4 mm" as the diameter of 1 opening. Similarly, when the second region is a region other than the discretely arranged first regions, the effective area of the second region can be obtained by extending 0.2mm outward (i.e., toward the first region) from the edge of the second region. The area ratio with respect to the protective layer is obtained using the effective area of the second region thus calculated, and the obtained value is the effective area ratio.

Since the desorbed gas does not remain at a high concentration between the filler 4 and the main surface 3a of the solar cell 3, the filler 4 may enter a part or all of the second regions 10 and 13. The shape of the second regions 10 and 13 is not particularly limited as long as the above requirements are satisfied.

(examples)

The present invention will be described in more detail with reference to the following examples.

The solar cell modules of examples 1 to 9 and comparative examples 1 to 3 were produced, and the characteristics of these solar cell modules were evaluated.

First, the structure and the manufacturing method of the solar cell module of each example and comparative example will be explained.

[ example 1]

The solar cell module of example 1 has the same structure as the solar cell module 100 shown in fig. 1A and 1B. The materials, sizes, and thicknesses of the respective constituent elements in the solar cell module of example 1 are shown below.

First substrate 1: doped SnO with fluorine₂Glass substrate for layer (0.7 mm thickness, surface resistance 10. omega./sq. made by Nitri Kogyo Co., Ltd.)

Electron transport layer 8: titanium oxide (thickness: 30nm), porous titanium oxide (thickness: 200nm)

Photoelectric conversion layer 6: CH (CH)₃NH₃PbI₃(thickness 300nm)

Hole transport layer 7: PTAA (manufactured by Aldrich Co.)

Second substrate 2: al deposited film (PET (thickness 50 μm)/Al (thickness 7 μm)/PET (thickness 50 μm))

Filling material 4: polyolefin (thickness 450 μm)

First region 9 of protective layer 5: polyimide tape (P-221: manufactured by Ridong electric engineering Co., Ltd.) (thickness 25 μm)

Second region 10 of protective layer 5: area ratio 10%, effective area ratio 24%, diameter of opening 0.71mm, center-to-center distance of opening 2mm

The method for manufacturing the solar cell module of example 1 is as follows.

Preparing SnO doped with fluorine on main surface₂A conductive glass substrate having a layer thickness of 0.7 mm. This was used as the first substrate 1. Further, the fluorine in the conductive glass substrate is doped with SnO₂The layer serves as a first electrode.

On the first electrode of the first substrate 1, a titanium oxide layer having a thickness of about 30nm and a porous titanium oxide layer having a thickness of 0.2 μm were formed as the electron transit layer 8. A titanium oxide layer was formed on the first electrode of the first substrate 1 by a sputtering method. The porous titanium oxide layer is formed by applying a titanium oxide slurry to the titanium oxide layer, drying the titanium oxide slurry, and then firing the dried film in air at 500 ℃ for 30 minutes. A titanium oxide slurry was prepared by dispersing high purity titanium oxide powder having an average 1-order particle diameter of 20nm in ethyl cellulose.

Next, the photoelectric conversion layer 6 is formed on the electron transport layer 8. Preparation of a composition containing PbI at a concentration of 1mol/L₂And a Dimethylsulfoxide (DMSO) solution containing methyl ammonium iodide at a concentration of 1 mol/L. The solution was coated on the electron transport layer 8 by spin coating, thereby forming a coating film. Then, the coating film formed was heat-treated on a hot plate at 130 ℃ to obtain a photoelectric conversion layer 6, i.e., CH having a perovskite structure₃NH₃PbI₃And (3) a layer.

Next, a toluene solution containing PTAA at a concentration of 10mg/mL, lithium bis (fluorosulfonyl) imide (LiTFSI) at a concentration of 5mmol/L, and tert-butylpyridine (tBP) at a concentration of 6 μ L/mL was applied on the photoelectric conversion layer 6 by spin coating, thereby obtaining a hole transport layer 7.

As a second electrode, 80nm of gold was vapor-deposited on the hole transport layer 7.

Through the above steps, the solar cell 3 is formed on the first substrate 1.

Next, the protective layer 5 is formed on the solar cell 3. A polyimide tape having a plurality of openings penetrating in the thickness direction and discretely arranged is prepared. Each opening has a circular shape with a diameter of 0.71 mm. The plurality of openings are formed so that the center-to-center spacing of the openings is 2 mm. The opening is formed by pushing a mold having conical projections arranged at equal intervals onto the polyimide tape. The area ratio of the openings in the protective layer 5, that is, the area ratio of the second region was 10%. The effective diameter of the opening is 1.11mm, which is 0.71mm +0.4 mm. The effective area ratio of the opening, that is, the effective area ratio of the second region was 24%. The polyimide tape having such an opening is disposed on the solar cell 3 to form the protective layer 5.

Next, a laminate body including the first substrate 1, an Al deposited film as the second substrate 2 provided at a position facing the first substrate 1, and a polyolefin sheet as the filler 4 disposed between the first substrate 1 and the second substrate 2 was subjected to thermal compression bonding by a vacuum lamination method, thereby obtaining the solar cell module 100. The pressure bonding was performed by degassing at 130 ℃ for 180 seconds and pressing the laminate for 300 seconds.

[ examples 2 to 8]

In the solar cell module of example 1, the diameters of the openings in the protective layer 5, the center-to-center distances of the openings, and the area ratios of the second regions were changed to the values shown in table 1, thereby producing the solar cell modules of examples 2 to 8.

[ example 9]

The solar cell module of example 9 has the same structure as the solar cell module 200 shown in fig. 2A and 2B. The solar cell module of example 9 was fabricated in the same manner as the solar cell module of example 1, except for the protective layer 11. Therefore, only the protective layer 11 of the solar cell module of example 9 will be described here.

In the protective layer 11 of the solar cell module of example 9, the first regions 12 covering the surface of the solar cell are discretely arranged. The same polyimide tape as the material for forming the protective layer 5 in example 1 was used for the first region 12. The polyimide tape was arranged in a stripe shape on the solar cell 3 so that the effective area ratio of the second region 13 became 33% and the width of the tape was 6.0mm and the discrete distance between the first regions 12 was 1.45 mm. As described later, the effective area ratio of the second region 13 is a value obtained when the effective distance is set to 0.2 mm.

Comparative example 1

The solar cell module of comparative example 1 has the same structure as the solar cell module 300 shown in fig. 3. A solar cell module of comparative example 1 was produced in the same manner as in example 1, except that the protective layer was not formed in the solar cell module of example 1.

Comparative example 2

The solar cell module of comparative example 2 has the same structure as the solar cell module 400 shown in fig. 4A and 4B. A solar cell module of comparative example 2 was produced in the same manner as in example 1, except that the opening portion was not formed in the protective layer of the solar cell module of example 1. That is, in comparative example 2, the protective layer was formed using a polyimide tape having no opening.

Comparative example 3

The solar cell module of comparative example 3 has the same structure as the solar cell module 500 shown in fig. 5A and 5B. The main surface of the solar cell was divided into two parts at the center, and a polyimide tape having no opening was disposed with one region being a first region. The other region is a second region of the protective layer without a polyimide tape.

[ evaluation method ]

The solar cell module was left to stand in an environment of 85 ℃ and a dew point of-30 ℃ for 300 hours (hereinafter referred to as "left to stand in a high-temperature environment for 300 hours"), and characteristics of the solar cell module before and after the solar cell module was left to stand were compared. Regarding the solar cell characteristics, a halogen lamp ("BPSX 300 BA" manufactured by spectrometer Co., Ltd.) was used to irradiate a solar cell module with 100mW/cm²The current-voltage characteristics after stabilization were measured using ALS440B manufactured by BAS. Thus, the open circuit voltage (Voc), Fill Factor (FF), and conversion efficiency in each solar cell were determined. The maintenance ratio of the characteristics of each solar cell is a relative value of each parameter after the solar cell is placed, assuming that each parameter before the solar cell is placed is 100. When the two-dimensional persistence of Voc and FF is 95% or more, it is determined that the effect is obtained. When the two-dimensional persistence of Voc and FF is 99% or more, it is determined that the effect is sufficient. The results are shown in Table 1.

TABLE 1

First, attention is paid to the maintenance ratio of FF. In the solar cell module of comparative example 1 in which the protective layer 5 was not provided, the maintenance ratio of FF was 49.8%. In the solar cell module of comparative example 1, FF was greatly reduced to about half by 300 hours of standing in a high-temperature environment. This is considered to be because the hole transport layer 7 of the solar cell 3 and the filler 4 are in contact with each other, and therefore peeling occurs at the interface between the photoelectric conversion layer 6 and the hole transport layer 7. In the solar cell modules of examples 1 to 8, the maintenance ratio of FF was 95% or more, and the effect on the maintenance ratio of FF was obtained. In the solar cell modules of examples 1 to 7 in which the area ratio of the second region satisfied 60% or less, the maintenance ratio of FF was 99% or more, and a sufficient effect of the maintenance ratio of FF was obtained. Fig. 6 is a diagram showing a relationship between the area ratio of the second region and the maintenance ratio of FF. The graph of fig. 6 is based on the maintenance ratios of FF of the solar cell modules of examples 1 to 4, 7 and 8 and the solar cell modules of comparative examples 1 and 2.

Next, attention is paid to the maintenance ratio of Voc. In the solar cell module of comparative example 2 having the area ratio of the second region of 0%, that is, having no protective layer of the second region, the maintenance ratio of Voc was less than 95%, and the maintenance ratio of Voc was not sufficient. The reason for this is considered to be that since the second region is not provided in the protective layer, it is difficult for the desorption gas to pass through the protective layer, and the desorption gas is retained at a high concentration on the surface of the solar cell. In the solar cell modules of examples 1 to 8, the maintenance ratio of Voc was 95% or more, and the effect of the maintenance ratio of Voc was obtained. In the solar cell modules of examples 1 to 6 and 8 in which the area ratio of the second region satisfied 7% or more, the maintenance ratio of Voc was 99% or more, and a sufficient effect of the maintenance ratio of Voc was obtained. Fig. 7 is a diagram showing a relationship between the area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 7 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 4, 7 and 8 and the solar cell module of comparative example 2.

Further, it is considered that in the solar cell module of comparative example 1, the Voc maintenance rate is greatly reduced although the area ratio of the second region is 100%, and the mechanism is different from the degradation due to the desorption gas because of the interfacial separation as described above. Fig. 8 is a diagram showing a relationship between the area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 8 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 4, 7 and 8 and the solar cell modules of comparative examples 1 and 2.

Next, attention is focused on the discrete arrangement of the second regions, which are the openings. In the solar cell module of comparative example 3 in which both the first region and the second region were continuously arranged together, the maintenance ratio of Voc was less than 99% although the area ratio of the second region was 50%. Fig. 9 is a diagram showing a relationship between the area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 9 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 4, 7 and 8 and the solar cell modules of comparative examples 2 and 3. The reason for this is considered to be that, in the region of the protective layer in the power generation region of the solar cell that is completely covered with the first region, the desorption gas is retained at the surface of the solar cell at a high concentration. Therefore, the necessity of discrete arrangement of the second regions was confirmed.

However, it is considered that if the distance to the opening, i.e., the second region is equal to or less than the effective distance, the retention of the desorbed gas can be suppressed. Then, in order to examine the effective distance, the "effective aperture area ratio" was calculated in consideration of the area including the region extending from the actual aperture to the effective distance, including examples 5 and 6 in which the distance between the aperture centers is different from that in the other examples, and the relationship with the Voc maintenance ratio was confirmed. The effective aperture area ratio was calculated by setting the effective distance to 0.2 mm.

Fig. 10 is a diagram showing a relationship between the area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 10 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 8 and the solar cell modules of comparative examples 2 and 3. Fig. 11 is a diagram showing a relationship between the effective area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 11 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 8 and the solar cell modules of comparative examples 2 and 3. As shown in fig. 10, examples 1 to 4 in which the opening center intervals were fixed at 2mm, and example 5 (opening center interval of 1mm) and example 6 (opening center interval of 4mm) in which the opening center intervals were different, a slight difference was found in the relationship between the area ratio of the second region and the maintenance ratio of Voc. On the other hand, as shown in fig. 11, the effective area ratio and the maintenance ratio of Voc of the second region of up to 0.2mm as the effective distance showed a very good correlation including examples 5 and 6 in which the opening center intervals were different. Therefore, it is considered that if the distance to the opening is 0.2mm or less, the retention of the desorption gas can be suppressed.

Fig. 12 is a diagram showing a relationship between the effective area ratio of the second region and the maintenance ratio of Voc. The graph of fig. 12 is based on the maintenance ratios of Voc of the solar cell modules of examples 1 to 9 and the solar cell module of comparative example 2. The solar cell module of example 9 and the solar cell modules of examples 1 to 8 differ in the form of the protective layer. However, as shown in fig. 12, the solar cell module of example 9 and the solar cell modules of examples 1 to 8 showed a very good correlation in terms of the effective area ratio of the second region and the maintenance ratio of Voc, which are considered as effective distances up to 0.2 mm.

Industrial applicability

The solar cell module of the present invention can be widely used as a device for a power generation system that electrically converts sunlight.

Description of the symbols:

1. 101 first substrate

2. 102 second substrate

3. 103 solar cell

3a major surface

4. 104 filler material

5. 11, 109, 110 protective layer

6. 106 photoelectric conversion layer

7. 107 hole transport layer

8. 108 electron transport layer

9. 12, 111 first region

10. 13, 112 second region

100. 200, 300, 400, 500 solar cell modules.