Thin-film solar battery pack and preparation method thereof

Abstract

The invention relates to a thin-film solar battery pack and a preparation method thereof. The thin-film solar battery pack provided by the invention comprises a plurality of effective power generation areas and a dead area located between any two adjacent effective power generation areas in the horizontal direction, and comprises a transparent electrode, a first charge transfer layer, a photoelectric conversion layer, a second charge transfer layer and a counter electrode which are sequentially overlapped in the vertical direction, a light storage part is arranged at a dead zone of one side, opposite to the first charge transmission layer, of the transparent electrode, and the light storage part is filled with a long afterglow material. According to the invention, the long-afterglow material is arranged in the dead zone of the module battery, so that the yield and efficiency of power generation of the solar battery are increased.

Description

Technical Field

[0001] The present application belongs to the field of batteries, and specifically relates to a thin-film solar cell group and a preparation method thereof. Background Art

[0002] With the rapid development of human society, the demand for energy in production and life is also increasing. The fossil energy currently used in large quantities has many problems such as environmental pollution and limited reserves. Therefore, it is urgent to vigorously develop new green, clean and renewable energy. Solar cells can convert inexhaustible solar energy into electrical energy for people to use, and have the potential to improve my country's energy structure as a new green renewable energy.

[0003] However, there is a problem with solar power generation that affects its convenience: it cannot generate electricity at night. Solar cells rely on sunlight for energy conversion. After sunset, there is no sunlight at night, and the power supply will be lost. However, even after sunset, there is still a huge demand for electricity in cities, and there is also a demand for electricity for lighting, heating, communications, etc. in rural streets. Existing energy storage technologies that rely on water storage or chemical battery storage have certain defects.

[0004] Long afterglow materials are materials that can emit light for a long time in the dark after being exposed to light. They are widely used in signboards, road signs, luminous toys, etc. At present, there are many high-performance long afterglow materials that can keep emitting light for up to 10 hours in the dark after being exposed to sunlight for more than ten minutes. Using this type of high-brightness long afterglow material, light energy can be accumulated during the day when there is sunlight, and light can be emitted at night after sunset to continue to maintain the power generation of solar cells. Combined with the current cheap and efficient perovskite solar cells, their higher photoelectric conversion efficiency in weak light can better utilize the afterglow at night to generate electricity, thereby achieving uninterrupted power supply day and night. It is a design solution with excellent application prospects for solar cell power supply at night.

[0005] The existing technology is applicable to dye-sensitized solar cells, which require the cell structure to be light-transmissive so that sunlight can pass through the cell and illuminate the long afterglow material on the back electrode. The method of adding long afterglow material inside the cell has restrictions on the cell structure. At the same time, the composition of the long afterglow material can easily affect the normal operation of the battery. Summary of the invention

[0006] In order to solve the above problems existing in the prior art, the present application proposes a thin-film solar cell group and a preparation method thereof. The present application achieves increased production and efficiency of solar cell power generation by placing a long afterglow material in the dead zone of the module cell.

[0007] In the first aspect, the present application provides a thin-film solar cell group, which includes multiple effective power generation areas and a dead area located between any two adjacent effective power generation areas in the horizontal direction, and the battery group includes a transparent electrode, a first charge transfer layer, a photoelectric conversion layer, a second charge transfer layer and a counter electrode stacked in sequence in the vertical direction, wherein a light storage portion is provided in the dead area on the side of the transparent electrode opposite to the first charge transfer layer, and the light storage portion is filled with a long afterglow material.

[0008] In some embodiments, the long afterglow material is selected from a mixed white light long afterglow material, and the mixed white light long afterglow material is selected from a first mixture consisting of a red long afterglow material, a yellow-green long afterglow material and a sky blue long afterglow material, or a second mixture consisting of a red long afterglow material and a blue-green long afterglow material, or a third mixture consisting of an orange long afterglow material and a blue-green long afterglow material.

[0009] In some embodiments, in the first mixture, the mass ratio of the yellow-green long afterglow material, the red long afterglow material and the sky blue long afterglow material is 1:(5-7):(1-3). In some embodiments, in the first mixture, the mass ratio of the yellow-green long afterglow material to the red long afterglow material is 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, 1:6.0, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9 or any value therebetween. In some embodiments, in the first mixture, the mass ratio of the yellow-green long afterglow material to the sky blue long afterglow material is 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or any value therebetween.

[0010] In some embodiments, the mass ratio of the yellow-green long afterglow material, the red long afterglow material and the sky blue long afterglow material is 1:(5.5-6.5):(1.5-2.5). In some embodiments, the mass ratio of the yellow-green long afterglow material, the red long afterglow material and the sky blue long afterglow material is 1:6:2.

[0011] In some embodiments, in the second mixture, the mass ratio of the blue-green long afterglow material to the red long afterglow material is 1:(3.5-5.5). In some embodiments, in the second mixture, the mass ratio of the blue-green long afterglow material to the red long afterglow material is 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4.0, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5.0, 1:5.1, 1:5.2, 1:5.3, 1:5.4 or any value therebetween.

[0012] In some embodiments, the mass ratio of the blue-green long afterglow material to the red long afterglow material is 1:(4-5). In some embodiments, the mass ratio of the blue-green long afterglow material to the red long afterglow material is 3:14.

[0013] In some embodiments, in the third mixture, the mass ratio of the blue-green long afterglow material to the orange long afterglow material is 1:(4-6). In some embodiments, in the third mixture, the mass ratio of the blue-green long afterglow material to the orange long afterglow material is 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5.0, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9 or any value therebetween.

[0014] In some embodiments, the mass ratio of the blue-green long afterglow material to the orange long afterglow material is 1:(4.5-5.5). In some embodiments, the mass ratio of the blue-green long afterglow material to the orange long afterglow material is 1:5.

[0015] The present application obtains a long afterglow material that can emit high-brightness mixed white light for a long time by mixing and blending long afterglow materials of different colors in a specific proportion, so as to imitate the mixed spectrum of sunlight, so that the solar cell can generate electricity at night under the irradiation of mixed light similar to that during the day, effectively improving the efficiency of the cell.

[0016] In some embodiments, a transparent semi-cylindrical shell is disposed at a dead zone on a side of the transparent electrode opposite to the first charge transport layer, and a cross section of the transparent semi-cylindrical shell contacts the transparent electrode to form a light storage portion.

[0017] The present application has a higher space utilization rate under the same area by adopting a light storage part with a semi-cylindrical structure.

[0018] In some embodiments, the material of the transparent shell is selected from transparent plastic.

[0019] In some embodiments, the ratio of the diameter of the semi-cylindrical shell to the dead zone length is (0.8-1.2):1, for example, 0.85:1, 0.9:1, 0.95:1, 1.05:1, 1.1:1, 1.15:1 or any thermally arbitrary value therebetween.

[0020] In some embodiments, the ratio of the height of the semi-cylindrical shell to the width of the thin-film solar cell group is (0.8-1.2):1, for example, 0.85:1, 0.9:1, 0.95:1, 1.05:1, 1.1:1, 1.15:1 or any thermal value therebetween.

[0021] In some embodiments, the thin film solar cell array is selected from a perovskite solar cell array.

[0022] In some embodiments, the transparent electrode is selected from fluorine-doped tin oxide and / or indium tin oxide.

[0023] In some embodiments, the first charge transport layer is an electron transport layer, and a material forming the first charge transport layer is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, carbon 60 and PCBM.

[0024] In some embodiments, the photoelectric conversion layer is selected from perovskite thin films.

[0025] In some embodiments, the second charge transport layer is a hole transport layer, and the material forming the second charge transport layer is selected from one or more of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), P3HT, PTAA, nickel oxide and phthalocyanine.

[0026] In some embodiments, the counter electrode is selected from one or more of a silver electrode, a gold electrode, and a graphite electrode.

[0027] In a second aspect, the present application provides a method for preparing the thin-film solar cell group according to the first aspect, which comprises the following steps:

[0028] S1: applying a slurry containing a long afterglow material into the light storage part;

[0029] S2: bonding the light storage part of step S1 to the dead area on the side of the transparent electrode opposite to the first charge transport layer.

[0030] In some embodiments, in step S1, the slurry further comprises a resin thickener and a dispersant. In some embodiments, the resin thickener is selected from one or more of polyacrylic resin, polystyrene resin and polycarbonate. In some embodiments, the dispersant is selected from one or more of dichloromethane, ethyl acetate and isopropanol.

[0031] In some embodiments, in step S1, based on the mass of the slurry, the mass content of the long afterglow material is 30%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or any value therebetween. In some embodiments, the mass content of the long afterglow material is 50%-70%.

[0032] In some embodiments, in step S1, based on the mass of the slurry, the mass content of the resin thickener is 5%-20%, for example, 6%, 8%, 10%, 11%, 13%, 15%, 17%, 19% or any value therebetween.

[0033] In some embodiments, in step S1, based on the mass of the slurry, the mass content of the dispersant is 10%-40%, for example, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%, 37% or any value therebetween.

[0034] In some embodiments, in step S2, the bonding is achieved by bonding slurry. In some embodiments, the bonding slurry is the slurry containing the long afterglow material.

[0035] In a third aspect, the present application provides an electrical device, which includes the thin-film solar cell group described in the first aspect or the thin-film solar cell group prepared by the preparation method described in the second aspect.

[0036] This application uses high-brightness long afterglow materials to design a light-absorbing energy storage structure in the dead zone of the module battery. The preparation is simple and does not damage the structure and stability of the battery itself. It cleverly utilizes the inactive area that is wasted during the operation of the battery to absorb light energy, and in the process of long afterglow material light absorption and light emission, the unused sunlight in the battery during the day is stored and released at night, so that the power generation time of the solar cell is extended to the night, the power generation of the solar cell is increased, and the solar cell can also provide electrical energy output at night without sunlight. Achieve increased production and efficiency of solar cell power generation. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 A schematic diagram of the structure of a perovskite solar cell group prepared according to some embodiments of the present application;

[0038] Among them, 1-dead zone, 2-light storage part, 3-transparent electrode, 4-first charge transport layer, 5-photoelectric conversion layer, 6-second charge transport layer, 7-counter electrode.

[0039] Figure 2 Schematic diagram of laser scribing of the perovskite solar cell group in Example 1 of the present application.

[0040] Figure 3 The fluorescence emission spectrum of the mixed white light long afterglow material used in Example 1 of the present application is shown.

[0041] Figure 4 The JV curve of the cell operation of the perovskite solar cell group prepared in Example 1 of the present application under 1 standard simulated sunlight is shown.

[0042] Figure 5 The JV curve of the cell operation under dark light of the perovskite solar cell group prepared in Example 1 of the present application is shown. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below in conjunction with the embodiments and drawings. The specific embodiments described herein are only used to explain the present application and are not intended to constitute any limitation to the present application. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concepts of the present disclosure. Such structures and technologies are also described in many publications.

[0044] The present application provides a thin film solar cell group, such as Figure 1 As shown, it includes multiple effective power generation areas and a dead zone 1 located between any two adjacent effective power generation areas in the horizontal direction, and the battery pack includes a transparent electrode 3, a first charge transport layer 4, a photoelectric conversion layer 5, a second charge transport layer 6 and a counter electrode 7 which are stacked in sequence in the vertical direction, wherein a light storage part 2 is provided in the dead zone on the side of the transparent electrode 1 opposite to the first charge transport layer 1, and the light storage part is filled with a long afterglow material.

[0045] In some embodiments, a transparent semi-cylindrical shell is disposed at the dead zone on the side of the transparent electrode 1 opposite to the first charge transport layer 4 , and a cross section of the transparent semi-cylindrical shell contacts the transparent electrode to form a light storage portion 2 .

[0046] In some embodiments, the ratio of the diameter of the semi-cylindrical shell to the dead zone length is (0.8-1.2):1.

[0047] In the present application, the length of the dead zone is the distance between two adjacent effective power generation areas in the horizontal direction.

[0048] In some embodiments, the ratio of the height of the semi-cylindrical shell to the width of the thin-film solar cell group is (0.8-1.2):1.

[0049] The present application will be further described below through specific embodiments, but the scope of the present application is not limited thereto.

[0050] Experimental instruments and materials

[0051] Laser etching machine: Wuhan Junwei Technology JW-20W-KS;

[0052] Spin coater: Wuhan Junwei Technology JW-A5;

[0053] Solar simulator: Newport;

[0054] Vacuum coating machine: Micro-nano vacuum VZZ-300;

[0055] Rare earth long afterglow powders and the like are commercially available reagents.

[0056] Test Method

[0057] First, the solar simulator is calibrated with a standard battery to 1.5AM light intensity. The prepared battery is placed under the irradiation of the solar simulator light source for testing. The source meter measures the current-voltage characteristic curve of the battery under standard conditions. Based on the curve, the battery performance parameters such as photoelectric conversion efficiency, open circuit voltage, short circuit current, and fill factor can be calculated.

[0058] Example 1

[0059] Preparation of blank perovskite solar cell array

[0060] In order to reduce the resistance of the transparent electrode, a series method is used to form components. Specifically, it is carried out through three laser scribing (P1, P2, P3). First, the P1 laser scribes the conductive glass substrate to separate the transparent electrodes on the conductive glass. Then deposit the electron transport layer (20 mg / mL lead sulfate ethanolamine solution), and scrape the perovskite layer and the hole layer (hole transport material Spiro-OMeTAD). Subsequently, P2 laser scribing separates the battery active layer. After evaporating the metal electrode, P3 laser scribing forms strips of module batteries. The areas where P1, P2, and P3 are scribed become dead areas because they cannot generate electricity, and the unscribed areas are active areas, see the schematic diagram Figure 2 .

[0061] The perovskite thin layer is prepared by combining scraping and flash evaporation. The perovskite precursor solution used is: PbI2 and MAI are dissolved in a mixed solvent of N-methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF), wherein the molar ratio of PbI2 and MAI is 1.2:1, and the volume ratio of NMP and DMF is 1:4. Then the precursor solution is spread on the substrate by scraping (the instrument model is Pushen, KTQ-200) to form a perovskite wet film, and the speed of the scraper relative to the substrate is 2mm / s. Then the wet film is transferred to a vacuum chamber, and the atmospheric pressure is reduced to 100Pa within 20 seconds, maintained for 2 minutes, and the film color gradually changes from transparent to black, and then it is transferred to a heating plate, annealed at 75℃ for 5 minutes, and then annealed at 125℃ for 10 minutes to form a perovskite polycrystalline film.

[0062] Preparation of long afterglow material slurry:

[0063] The commercially available red long afterglow material, yellow-green long afterglow material and sky blue material were mixed and stirred in a mass ratio of 6:1:2 to obtain white luminous powder. The fluorescence emission spectrum of the white luminous powder is as follows: Figure 3 shown.

[0064] The white luminous powder is mixed with polyacrylic acid resin and ethyl acetate dispersant to obtain a long afterglow slurry, wherein based on the mass of the long afterglow slurry, the mass content of the white luminous powder is 60%, the mass content of the acrylic resin is 13%, and the mass content of the dispersant is 37%.

[0065] Preparation of light storage part:

[0066] Take a semi-cylindrical transparent plastic shell (the diameter of the shell is the same as the horizontal length of the dead zone at the transparent electrode surface, and the height of the shell is the same as the width of the perovskite solar cell group to ensure that the light storage part can completely cover the dead zone), and fill the above-mentioned long afterglow material slurry into the semi-cylindrical shell.

[0067] A layer of slurry (long afterglow slurry) is brushed on the connection, and the prepared light storage part is attached to the dead area of ​​the transparent electrode surface of the blank perovskite solar cell group to obtain the perovskite solar cell group.

[0068] The perovskite solar cell group with a light storage unit prepared above was tested under a solar simulator to determine the output power of the cell under standard simulated sunlight and dark light.

[0069] 1 Standard JV curve of battery working under simulated sunlight is as follows Figure 4 As shown, from Figure 4 It can be seen that the maximum output power of the battery under standard simulated sunlight is 332.6 mW

[0070] The JV curve of the battery working under dim light is as follows Figure 5 As shown, from Figure 5 It can be seen that the maximum output power of the battery under dim light is 79.44 mW.

[0071] Example 2

[0072] Preparation of blank perovskite solar cells: same as in Example 1.

[0073] Preparation of long afterglow material slurry: Mix and stir the commercially available orange long afterglow material and blue-green long afterglow material in a mass ratio of 5:1 to obtain white luminous powder. The rest is the same as in Example 1.

[0074] Preparation of light storage unit and perovskite solar cell group: same as Example 1.

[0075] The perovskite solar cell group with a light storage unit prepared above was tested for output power under standard simulated sunlight and dark light under a solar simulator, and the maximum output powers were 328.8 mW and 34.48 mW, respectively.

[0076] Example 3

[0077] Preparation of blank perovskite solar cells: same as in Example 1.

[0078] Preparation of long afterglow material slurry: Mix and stir the commercially available red long afterglow material and blue-green long afterglow material in a mass ratio of 14:3 to obtain white luminous powder. The rest is the same as in Example 1.

[0079] Preparation of light storage unit and perovskite solar cell group: same as Example 1.

[0080] The perovskite solar cell group with a light storage unit prepared above was tested for output power under standard simulated sunlight and dark light under a solar simulator, and the maximum output powers were 339.3 mW and 41.08 mW, respectively.

[0081] Example 4

[0082] Preparation of blank perovskite solar cells: same as in Example 1.

[0083] Preparation of long afterglow material slurry: The only difference is that based on the mass of the long afterglow slurry, the mass content of the white luminous powder is 30%.

[0084] Preparation of light storage unit and perovskite solar cell group: same as Example 1.

[0085] The perovskite solar cell group with a light storage unit prepared above was tested for output power under standard simulated sunlight and dark light under a solar simulator, and the maximum output powers were 301.7 mW and 13.29 mW, respectively.

[0086] Example 5

[0087] Preparation of blank perovskite solar cells: same as in Example 1.

[0088] Preparation of long afterglow material slurry: The only difference is that based on the mass of the long afterglow slurry, the mass content of the white luminous powder is 80%.

[0089] Preparation of light storage unit and perovskite solar cell group: same as Example 1.

[0090] The perovskite solar cell group with a light storage unit prepared above was tested for output power under standard simulated sunlight and dark light under a solar simulator, and the maximum output powers were 279.3 mW and 46.76 mW, respectively.

[0091] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, the technical solution of the present application can be subjected to a variety of simple modifications, including combining various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed in the present application and belong to the protection scope of the present application.

Claims

1. A thin-film solar cell group, which comprises a plurality of effective power generation areas and a dead area between any two adjacent effective power generation areas in the horizontal direction, and the cell group comprises a transparent electrode, a first charge transport layer, a photoelectric conversion layer, a second charge transport layer and a counter electrode in a sequentially stacked manner in the vertical direction, wherein: A light storage portion is provided at a dead zone on a side of the transparent electrode opposite to the first charge transport layer, and the light storage portion is filled with a long afterglow material.

2. The thin-film solar cell group according to claim 1, characterized in that: The long afterglow material is selected from a mixed white light long afterglow material, and the mixed white light long afterglow material is selected from a first mixture consisting of a red long afterglow material, a yellow-green long afterglow material and a sky blue long afterglow material, or a second mixture consisting of a red long afterglow material and a blue-green long afterglow material, or a third mixture consisting of an orange long afterglow material and a blue-green long afterglow material.

3. The thin-film solar cell group according to claim 2, characterized in that: In the first mixture, the mass ratio of the yellow-green long afterglow material, the red long afterglow material and the sky blue long afterglow material is 1:(5-7):(1-3), preferably 1:(5.5-6.5):(1.5-2.5); and / or In the second mixture, the mass ratio of the blue-green long afterglow material to the red long afterglow material is 1:(3.5-5.5), preferably 1:(4-5); and / or In the third mixture, the mass ratio of the blue-green long afterglow material to the orange long afterglow material is 1:(4-6), preferably 1:(4.5-5.5).

4. The thin-film solar cell group according to any one of claims 1 to 3, characterized in that: A transparent semi-cylindrical shell is provided at a dead zone on a side of the transparent electrode opposite to the first charge transport layer, and a cross section of the transparent semi-cylindrical shell contacts the transparent electrode to form a light storage portion; Preferably, the material of the transparent shell is selected from transparent plastic.

5. The thin-film solar cell group according to claim 4, characterized in that: The ratio of the diameter of the semi-cylindrical shell to the length of the dead zone is (0.8-1.2):1; and / or The ratio of the height of the semi-cylindrical shell to the width of the thin-film solar cell group is (0.8-1.2):

1.

6. The thin-film solar cell group according to any one of claims 1 to 5, characterized in that: The thin film solar cell group is selected from a perovskite solar cell group; Preferably, the transparent electrode is selected from fluorine-doped tin oxide and / or indium tin oxide, and / or, The first charge transport layer is an electron transport layer, and the material forming the first charge transport layer is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, carbon 60 and PCBM, and / or The photoelectric conversion layer is selected from a perovskite film, and / or The second charge transport layer is a hole transport layer, and the material forming the second charge transport layer is selected from one or more of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, P3HT, PTAA, nickel oxide and phthalocyanine, and / or The counter electrode is selected from one or more of a silver electrode, a gold electrode and a graphite electrode.

7. A method for preparing a thin-film solar cell group according to any one of claims 1 to 6, comprising the following steps: S1: applying a slurry containing a long afterglow material into the light storage part; S2: bonding the light storage part of step S1 to the dead area on the side of the transparent electrode opposite to the first charge transport layer.

8. The preparation method according to claim 7, characterized in that: In step S1, the slurry further comprises a resin thickener and a dispersant, preferably, the resin thickener is selected from one or more of polyacrylic acid resin, polystyrene resin and polycarbonate, and the dispersant is selected from one or more of dichloromethane, ethyl acetate and isopropanol; and / or Based on the mass of the slurry, the mass content of the long afterglow material is 30%-80%, preferably 50%-70%, and / or the mass content of the resin thickener is 5%-20%, and the mass content of the dispersant is 10%-40%.

9. The preparation method according to claim 7 or 8, characterized in that: In step S2, the bonding is achieved by bonding slurry. Preferably, the bonding slurry is the slurry containing the long afterglow material.

10. An electrical device comprising the thin-film solar cell group according to any one of claims 1 to 6 or the thin-film solar cell group prepared by the preparation method according to any one of claims 7 to 9.

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