A recycling method of a crystalline silicon perovskite tandem solar cell and the cell

Abstract

The application provides a recycling method of a crystalline silicon perovskite laminated solar cell, and belongs to the technical field of photovoltaic cell recycling. The method comprises the following steps: collecting an aged and scrapped perovskite / silicon laminated tandem solar cell including a single tandem cell or a tandem photovoltaic module; mechanically delaminating an encapsulating material and glass by heating; performing a physical cleaning process to separate and extract functional components; and finally recycling a functional silicon solar cell from the tandem cell. The silicon bottom cell recycled by the method can maintain good performance characteristics, the recycling effect is remarkable, the loss of raw materials and coating equipment is reduced, and the cost is reduced.

Description

Technical Field

[0001] This invention belongs to the field of photovoltaic cell recycling technology, specifically relating to a method and cell for recovering silicon-based cells with normal lossless energy conversion efficiency from waste perovskite / silicon tandem solar cells using thermal separation and chemical cleaning processes. Background Technology

[0002] To improve power conversion efficiency (PCE) and reduce the levelized cost of electricity (LCOE), perovskite / silicon tandem solar cells have been extensively studied, with a certified record PCE of 33.7%, far exceeding that of crystalline silicon solar cells. The high PCE achieved at low cost by perovskite / silicon tandem cells is a powerful driver for reducing the LCOE of photovoltaic systems. Despite high device efficiency and low manufacturing cost, the long-term stability of tandem cells remains one of the main challenges for this technology. The lower stability of tandem cells is mainly due to the segregation of halide phases in the wide-bandgap perovskite sub-cells; even the best stability of single-junction perovskite solar cells is still inferior to that of silicon solar cells. Silicon cells have an average lifespan of 20-25 years, and the lifespan is even longer in perovskite / silicon tandem structures because the wide-bandgap perovskite sub-cells can block ultraviolet radiation and reduce the total light intensity by half. Therefore, even if the stability of wide-bandgap perovskite solar cells can be improved to 20-25 years in the near future, the bottom silicon cell can still be reused at the end of the perovskite / silicon tandem cell's lifespan. Recycling and reusing the silicon bottom cell is an effective solution for reducing costs.

[0003] In recent years, the recycling of silicon photovoltaic modules has received increasing attention because it can shorten the cost recovery period. Currently, the main method for recycling silicon cells is to dissolve the perovskite layer with a solution to obtain the underlying silicon cell. For example, invention patent CN114871254B and the literature ACS Energy Lett. 2023, 8, 3, 1639–1644 use polar solvents such as dimethylformamide (DMF) and iodide solutions to dissolve the perovskite film and remove the aged perovskite sub-cells. Both methods involve chemical reactions that lead to the formation of byproducts, increasing the difficulty of cleaning the textured silicon surface and reducing the energy conversion efficiency of the recycled silicon bottom cell. During the process of using DMF to clean the perovskite material in the tandem cell, the C=O and Pb in the DMF react... 2+ The weakening of ion interactions leads to the adhesion of lead iodide, a degradation product of perovskite, to the surface of the silicon substrate cell, which is difficult to remove even with ultrasonic cleaning in DMF. Furthermore, the additional reaction materials required to dissolve the perovskite increase recycling costs. Therefore, there is a need to develop a method for completely stripping the perovskite sub-cells and recovering the silicon substrate cell without chemically reacting with the perovskite component in the perovskite / silicon tandem cell. Summary of the Invention

[0004] Given that existing technologies cannot completely remove the perovskite layer, recover the silicon base cell portion (excluding the perovskite sub-cells) in a perovskite / silicon tandem solar cell, and maintain its energy conversion efficiency, the present invention aims to provide a method for recovering the silicon base cell from a perovskite / silicon tandem solar cell while maintaining its original energy conversion efficiency for reuse. Unlike other methods for recovering silicon base cells, this method uses a solvent that cannot dissolve the perovskite material to dissolve the physical connection between the perovskite sub-cells and the silicon base cell in the tandem solar cell, namely the hole transport layer of the perovskite sub-cell, achieving the effect of completely peeling off the perovskite film to obtain the bare silicon base cell. In this recovery method, all participating raw materials do not need to react with the perovskite, no perovskite dissolution byproducts are generated, the surface cleaning of the silicon base cell is easy, and the raw material cost is low.

[0005] The first aspect of this invention provides a method for recycling crystalline silicon perovskite tandem solar cells. This method involves collecting aged and discarded perovskite / silicon tandem solar cells, including individual series cells or series photovoltaic modules, then mechanically delaminating the encapsulation material and glass through heating, followed by a physical cleaning process to separate and extract functional components. Finally, a fully functional silicon solar cell is recovered from the series cells. Specifically, the method includes the following steps:

[0006] (1) Provide a packaged series battery, wherein the packaged series battery comprises, from bottom to top, a silicon bottom battery, an organic hole transport layer, a perovskite absorber layer, an electron transport layer, a top electrode and a packaged glass, and the packaged glass is first removed from the packaged series battery by heat treatment to obtain an unpackaged series battery.

[0007] The silicon-based solar cell includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer;

[0008] (2) Then the unencapsulated series battery is immersed in an organic solvent at room temperature. After the organic hole transport layer dissolves, the perovskite absorber layer naturally detaches from the silicon bottom battery and floats in the organic solvent, thus obtaining the silicon bottom battery.

[0009] (3) The separated silicon bottom battery is rinsed with solvent more than twice, and then the silicon bottom battery is transferred to a hot plate for heating and annealing.

[0010] Furthermore, the equipment used for heat treatment in step (1) includes, but is not limited to, a heating table, an oven, and a hot air gun, with a heat treatment temperature range of 100~350 ℃ and a heat treatment time range of 1~60 min. The purpose of step (1) is to remove the outer encapsulation glass of the encapsulated series cells so that the solvent can better penetrate the perovskite absorber layer and the silicon bottom cell interface. At the same time, the heat treatment method will not damage the silicon crystal structure, ensuring the normal efficiency of the silicon bottom cell.

[0011] Furthermore, in step (2), the organic solvent is chlorobenzene (CB), the immersion time is 0-24 h, and the organic hole transport layer is composed of at least one of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD). In step (2), when the unencapsulated series battery is immersed in the organic solvent, the organic hole transport layer gradually dissolves, and the perovskite absorber layer, with the top electrode as its framework, adheres to the top battery and completely detaches from the silicon bottom battery. In a pin-type perovskite / silicon tandem solar cell, the perovskite sub-cell layer is located on top of the silicon base cell, and an organic hole transport layer serves as the connection between the perovskite and the silicon base cell to form the tandem cell. In the method described, an organic solvent dissolves the organic hole transport layer material of the connection portion without dissolving the perovskite material. Subsequently, the perovskite layer is completely detached, achieving the effect of obtaining a silicon base cell with an intact surface and no residual perovskite material.

[0012] Furthermore, in step (3), the solvent is chlorobenzene, the heating annealing temperature is 100~650 ℃, and the heating annealing time is 0~12 h.

[0013] The present invention also provides a battery prepared from a silicon-based battery obtained by the above-described recycling method, comprising, from bottom to top: a silicon-based battery, a top electrode, and an encapsulation glass;

[0014] The silicon-based solar cell includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer;

[0015] In one embodiment, the silicon bottom cell and the top electrode further include an organic hole transport layer, a perovskite absorber layer, and an electron transport layer, forming a crystalline silicon perovskite tandem solar cell structure.

[0016] The organic hole transport layer is composed of at least one of the following materials: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD).

[0017] In other embodiments, an inorganic hole transport layer is disposed between the silicon bottom battery and the organic hole transport layer, that is, the silicon bottom battery with the inorganic hole transport layer attached to its surface is obtained by the above-described recycling process, and the inorganic hole transport layer is nickel oxide (NiO). x ), molybdenum oxide (MoO) x It consists of at least one of cuprous iodide (CuI) and cuprous thiocyanate (CuSCN).

[0018] The perovskite absorber layer has an ABX3 structure, with an organic cation at the A site, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + CH3CH2NH3 + or Cs + At least one of them; the B site is a metal cation, including Pb 2+ Sn 2+ At least one of them; the X-position is a halide anion, including F - Cl - ,Br - I - At least one of the following. The organic solvent includes at least one of ethanol, isopropanol, methanol, dimethylformamide (DMF), G-butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N,N-dimethylacetamide.

[0019] The electron transport layer is composed of zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide (TiO2), and [6,6]-phenyl C61-butyrate methyl ester (PC). 61 BM), C60 (C 60 At least one of ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

[0020] The top electrode is at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon (C).

[0021] The recycling method for crystalline silicon perovskite tandem solar cells provided by this invention has the following advantages: 1) The solvent used in the recycling method does not dissolve the perovskite layer material, and does not generate additional byproducts due to damage to the perovskite crystal structure, thus reducing the difficulty of cleaning the silicon base cell surface and lowering costs; 2) The silicon base cell recycling step does not damage the silicon cell or reduce its energy conversion efficiency; 3) When the recycled silicon base cell is reused to manufacture tandem cells, there is no need to redeposit the inorganic hole transport layer, reducing raw material consumption and coating equipment wear. Attached Figure Description

[0022] Figure 1 A schematic diagram of the process flow for recycling a crystalline silicon perovskite tandem solar cell with a single hole transport layer provided by the present invention.

[0023] Figure 2 A schematic diagram of the process flow for recycling a crystalline silicon perovskite tandem solar cell with a dual hole transport layer provided by the present invention.

[0024] Figure 3 A schematic diagram of a battery structure provided by the present invention;

[0025] Figure 4 The JV curves of crystalline silicon solar cells in Embodiment 1, Comparative Example 1, and Comparative Example 2 of the present invention under AM 1.5G standard sunlight are shown.

[0026] Figure 5 Box plots showing the short-circuit current, open-circuit voltage, fill factor, and power conversion efficiency of crystalline silicon solar cells in Example 1 and Comparative Example 1 of this invention.

[0027] 100. Encapsulation glass; 210. Top electrode; 220. Electron transport layer; 230. Perovskite absorber layer; 250. Inorganic hole transport layer; 240. Organic hole transport layer; 300. Silicon substrate cell. Detailed Implementation

[0028] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of this application.

[0029] It should be noted that when a component is referred to as being "fixed to" or "set on" another component, it can be directly on or indirectly on that other component. When a component is referred to as being "connected to" another component, it can be directly connected to or indirectly connected to that other component.

[0030] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise expressly specified. "Several" means one or more, unless otherwise expressly specified.

[0031] In the description of this application, it should be understood that the terms "center", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0032] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0033] Throughout this specification, reference to "an embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment of this application. Therefore, the phrase "in one embodiment" or "in some embodiments" appears in various places throughout the specification, and not all references are to the same embodiment. Furthermore, in one or more embodiments, particular features, structures, or characteristics may be combined in any suitable manner.

[0034] This invention provides a method for recycling crystalline silicon perovskite tandem solar cells. The method described in this invention is mainly applied to crystalline silicon perovskite tandem solar cells with an organic hole transport layer. Traditional methods for recycling crystalline silicon bottom cells involve dissolving the perovskite absorber layer to remove the perovskite top cell. However, this method results in byproducts from the dissolution of the perovskite absorber layer, such as lead iodide, adhering to the surface of the silicon bottom cell. These byproducts are not only difficult to remove but also reduce the performance of the recycled silicon bottom cell.

[0035] In conventional tandem solar cells, a textured surface is often created on the silicon substrate to increase overall light absorption efficiency. However, this textured surface significantly increases the difficulty of recycling and cleaning. Byproducts from traditional solvent-based methods of dissolving the perovskite absorber layer easily deposit within the textured surface and are difficult to remove. This invention utilizes chlorobenzene (CB), an organic solvent, to dissolve the organic hole transport layer between the silicon substrate and the perovskite substrate. Chlorobenzene is incompatible with the perovskite absorber layer, thus preventing the generation of byproducts such as lead iodide and ensuring the cleanliness of the resulting silicon substrate surface.

[0036] Meanwhile, the recycling method described in this invention can also be applied to the recycling of crystalline silicon bottom cells in perovskite / crystalline silicon tandem solar cells with dual hole transport layers. Between the silicon bottom cell and the organic hole transport layer are structures such as a tunneling layer and an inorganic hole transport layer. The tunneling layer and the inorganic hole transport layer are composed of inorganic materials and will not be dissolved by chlorobenzene solvent. During cleaning, direct contact between the lower silicon bottom cell and the dissolving solvent can be reduced, minimizing damage to the silicon bottom cell and improving the performance of the recycled silicon bottom cell. Furthermore, the tunneling layer and inorganic hole transport layer above the silicon bottom cell can be directly applied to the fabrication of new perovskite tandem solar cells, reducing production costs.

[0037] Please see Figure 1 This invention involves collecting aged and discarded perovskite / silicon tandem solar cells, then mechanically delaminating the encapsulation material and glass through heating to dissolve the organic hole transport layer 240 in the tandem solar cells. A physical cleaning process is then used to separate and extract the functional components. Finally, a fully functional silicon bottom cell 300 is recovered from the tandem cells. Specifically, the steps include:

[0038] (1) Provide a packaged series battery, the packaged series battery comprising, from bottom to top, a silicon bottom battery 300, an organic hole transport layer 240, a perovskite absorber layer 230, an electron transport layer 220, a top electrode 210 and a packaged glass 100, and firstly remove the packaged glass 100 from the packaged series battery by heat treatment to obtain an unpackaged series battery.

[0039] The silicon substrate cell 300 includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer;

[0040] (2) Then the unencapsulated series battery is immersed in an organic solvent at room temperature. After the organic hole transport layer 240 dissolves, the perovskite absorber layer 230 naturally detaches from the silicon bottom battery 300 and floats in the organic solvent, thus obtaining the silicon bottom battery 300.

[0041] (3) The separated silicon bottom battery 300 is rinsed with solvent more than twice, and then the silicon bottom battery 300 is transferred to a hot plate for heating and annealing to remove residual solvent.

[0042] Furthermore, the equipment used for heat treatment in step (1) includes, but is not limited to, a heating table, an oven, and a hot air gun, with a heat treatment temperature range of 100~350 ℃ and a heat treatment time range of 1~60 min. The purpose of step (1) is to remove the external encapsulation glass 100 of the encapsulated series battery. The encapsulation glass 100 is fixed above the top electrode 210 by encapsulating adhesive, which protects the battery. During the cleaning process, heat treatment of this structure can soften the encapsulating adhesive, thereby allowing the encapsulation glass 100 to be peeled off, so that the solvent can better penetrate into the interface between the perovskite absorber layer 230 and the silicon bottom battery 300. At the same time, the heat treatment method will not damage the silicon crystal structure, ensuring the normal efficiency of the silicon bottom battery 300.

[0043] Furthermore, in step (2), the organic solvent is chlorobenzene (CB), the soaking time is 0-24 h, and the organic hole transport layer 240 is composed of at least one of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD). In step (2), when the unencapsulated series battery is immersed in the organic solvent, the organic hole transport layer 240 gradually dissolves, and the perovskite absorber layer 230 does not dissolve in the chlorobenzene solvent. The top electrode 210 serves as the framework and is attached to the top battery 210, thus completely separating from the silicon bottom battery 300.

[0044] In a pin-type perovskite / silicon tandem solar cell, the perovskite sub-cell layer is located on top of the silicon base cell 300. An organic hole transport layer 240 serves as the connection between the organic hole transport layer 240 and the silicon base cell 300 to form a tandem cell. In the method described, an organic solvent dissolves the organic hole transport layer 240 material in the connection portion without dissolving the perovskite absorber layer 230. Subsequently, the perovskite absorber layer 230 can be completely detached without producing byproducts such as lead iodide adhering to the silicon base cell 300 due to decomposition, resulting in a silicon base cell 300 with an intact surface and no residue.

[0045] Furthermore, in step (3), the solvent is chlorobenzene, the heating annealing temperature is 100~650 ℃, and the heating annealing time is 0~12 h. This further removes the film residue of the organic hole transport layer 240 after step (2), reducing the light absorption loss on the surface of the silicon bottom cell 300, or avoiding the increase in non-radiative recombination at the interface defects of the organic hole transport layer 240 during the recycling and remanufacturing of perovskite / silicon tandem cells, thereby obtaining a silicon bottom cell 300 with no loss of energy conversion efficiency.

[0046] Please see Figure 2 The recycling method described in this invention can also be applied to crystalline silicon perovskite tandem solar cells with a dual hole transport layer, including the following steps:

[0047] (1) Provide a packaged series battery, the structure of which from bottom to top includes: silicon bottom battery 300, inorganic hole transport layer 250, organic hole transport layer 240, perovskite absorber layer 230, electron transport layer 220, top electrode 210, and encapsulation glass 100. The encapsulation glass 100 is removed from the packaged series battery by heat treatment to obtain an unencapsulated series battery.

[0048] The silicon substrate cell 300 includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer;

[0049] (2) Immerse the unencapsulated series battery in an organic solvent at room temperature. After the organic hole transport layer 240 dissolves, the perovskite absorber layer 230 naturally floats in the organic solvent, resulting in a silicon bottom battery 300 with an inorganic hole transport layer 250 on the top surface.

[0050] (3) The silicon bottom cell 300 with an inorganic hole transport layer 250 on the top surface is rinsed with solvent more than twice, taken out and removed by heating and annealing to remove the residual solvent on the surface of the inorganic hole transport layer 250 and the bottom surface of the bottom electrode.

[0051] Furthermore, the equipment used for heat treatment in step (1) includes, but is not limited to, a heating table, an oven, and a hot air gun, with a heat treatment temperature range of 100~350 ℃ and a heat treatment time range of 1~60 min. The purpose of step (1) is to remove the outer encapsulation glass 100 of the encapsulated series battery so that it can better penetrate the interface between the perovskite absorber layer 230 and the inorganic hole transport layer 250 with the solvent. At the same time, the heat treatment method will not damage the silicon crystal structure and will ensure the normal efficiency of the silicon bottom battery 300.

[0052] Further, the organic solvent in step (2) is chlorobenzene (CB), and the immersion time is 0-24 h; the organic hole transport layer 240 is composed of at least one of the following: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD); the inorganic hole transport layer is nickel oxide (NiO). x ), molybdenum oxide (MoO) x It consists of at least one of cuprous iodide (CuI) and cuprous thiocyanate (CuSCN).

[0053] In step (2), the organic solvent dissolves the organic polymers or small molecule hole transport layer material in the perovskite / silicon tandem cell, but does not dissolve the inorganic hole transport layer 250 on top of the silicon substrate 300. When the recycled silicon substrate 300 is reused to manufacture a perovskite / silicon tandem cell, there is no need to additionally sputter the inorganic hole transport layer 250 on the silicon substrate surface compared to conventional process steps.

[0054] Furthermore, in step (3), the solvent is chlorobenzene, the annealing temperature is 100~650 ℃, and the annealing time is 0~12 h.

[0055] Please see Figure 3 The present invention also provides a battery prepared from a silicon-based battery obtained by the above-mentioned recycling process, comprising, from bottom to top: a silicon-based battery 300, a top electrode 210, and an encapsulation glass 100;

[0056] The silicon substrate cell 300 includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer;

[0057] In one embodiment, between the silicon bottom cell 300 and the top electrode 210, there is also an organic hole transport layer 240, a perovskite absorber layer 230, and an electron transport layer 220, forming a crystalline silicon perovskite tandem solar cell structure.

[0058] The organic hole transport layer 240 is composed of at least one of the following materials: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD).

[0059] The perovskite absorber layer 230 has an ABX3 structure, with an organic cation at the A site, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + CH3CH2NH3 + or Cs + At least one of them; the B site is a metal cation, including Pb 2+ Sn 2+ At least one of them; the X-position is a halide anion, including F - Cl - ,Br - I - At least one of the following. The organic solvent includes at least one of ethanol, isopropanol, methanol, dimethylformamide (DMF), G-butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N,N-dimethylacetamide.

[0060] The electron transport layer 220 is composed of zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide (TiO2), and [6,6]-phenyl C61-butyrate methyl ester (PC). 61 BM), C60 (C 60 At least one of ), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

[0061] The top electrode 210 is at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon (C).

[0062] In other embodiments, a tunneling layer 260 and an inorganic hole transport layer 250 are disposed between the silicon bottom cell 300 and the organic hole transport layer 240. That is, the silicon bottom cell 300 with the tunneling layer 260 and the inorganic hole transport layer 250 attached to its surface is obtained by the above-described recycling method. The tunneling layer 260 can be composed of oxides such as silicon dioxide, and can generate tunneling current at the contact points of the stacked cells, connecting the two sub-cells. The inorganic hole transport layer 250 is nickel oxide (NiO). x ), molybdenum oxide (MoO) x It is composed of at least one of cuprous iodide (CuI) and cuprous thiocyanate (CuSCN); at the same time, when fabricating a tandem cell on a silicon bottom cell 300 having the tunneling layer 260 and the inorganic hole transport layer 250 on the top surface, a perovskite absorber layer 230 can also be directly placed on the inorganic hole transport layer 250, reducing the fabrication process and lowering the cost.

[0063] To verify that the silicon-based solar cell obtained by the recycling method of the crystalline silicon perovskite tandem solar cell described in this embodiment of the invention has better performance, several embodiments and comparative examples are provided below to test the tandem solar cell obtained by this method.

[0064] Example 1:

[0065] This embodiment 1 provides a discarded crystalline silicon perovskite tandem solar cell, which uses chlorobenzene (CB) solvent to dissolve Cs. 0.22 FA 0.78 Pb(I 0.85 Br 0.15 The silicon-based solar cell with an a-Si:H(n) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(p) / ITO / Ag structure obtained by using a poly(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA) hole transport layer in a 3 / c-Si tandem solar cell includes the following steps:

[0066] (1) Place the scrapped perovskite / silicon tandem solar cell on a heating table and heat it at 180 °C for 10 min to dissolve the encapsulating adhesive and remove the encapsulating glass. This low-temperature annealing process will not damage the crystalline silicon solar cell.

[0067] (2) Remove the unencapsulated perovskite / silicon tandem solar cell from the heating stage and cool it to room temperature. Then immerse the unencapsulated perovskite / silicon tandem solar cell in 99.9% pure CB solvent for 30 min. After the PTAA hole transport layer material dissolves, remove the silicon bottom solar cell with the a-Si:H(n) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(p) / ITO / Ag structure from the solvent.

[0068] (3) The obtained silicon bottom cell was rinsed twice or more with 99.9% pure CB solvent, and then transferred to a hot plate and annealed at 150 °C for 10 min.

[0069] Comparative Example 1: This Comparative Example 1 provides a complete silicon-based solar cell structure, which has the same a-Si:H(n) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(p) / ITO / Ag structure as Embodiment 1. The silicon-based solar cell structure has not undergone the deposition and recycling process steps of hole transport layer, perovskite layer, electron transport layer and top electrode.

[0070] Comparative Example 2:

[0071] This comparative example provides a discarded crystalline silicon perovskite tandem solar cell, for which Cs is dissolved using dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvents. 0.22 FA 0.78 Pb(I 0.85 Br 0.15 Cs in 3 / c-Si tandem solar cells 0.22 FA 0.78 Pb(I 0.85 Br 0.15 The silicon-based solar cell with an a-Si:H(n) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(p) / ITO / Ag structure obtained by adding a perovskite layer and a PTAA hole transport layer specifically includes the following steps:

[0072] (1) Place the scrapped perovskite / silicon tandem battery on a heating table and heat it at 180 ℃ for 10 min to dissolve the encapsulating adhesive and remove the encapsulating glass.

[0073] (2) The unencapsulated tandem cells were then immersed in a mixed solvent of DMF and DMSO (mixing ratio of 4:1, volume ratio) and sonicated for 30 min. The perovskite layer, electron transport layer and top electrode can be removed during this process.

[0074] (3) The organic hole transport layer (poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA) was further removed by ultrasonic cleaning in a toluene bath. The solar cell with the a-Si:H(n) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(p) / ITO / Ag bottom cell structure was then removed from the solvent.

[0075] The JV curves of Example 1, Comparative Example 1, and Comparative Example 2 were measured under AM 1.5 G standard sunlight, as follows: Figure 4As shown in Table 1, the energy conversion efficiency (ECE) of the freshly manufactured crystalline silicon solar cell in Comparative Example 1 is 19.56%, while the ECE of the crystalline silicon solar cell recovered using this method in Example 1 is 19.01%, and the ECE of the crystalline silicon solar cell obtained using the conventional recovery method is 15.24%. Compared to the freshly manufactured crystalline silicon solar cell, the short-circuit current (Jsc), fill factor (FF), and power conversion efficiency (PCE) of the crystalline silicon solar cell obtained through the recovery method are almost not reduced, demonstrating the feasibility and effectiveness of the recovery method in this invention. The performance parameters of the solar cells are shown in Table 1 and... Figure 5 As shown.

[0076] Table 1. Solar cell performance parameters of Example 1, Comparative Example 1, and Comparative Example 2

[0077] sample Open circuit voltage (V) <![CDATA[Short-circuit current (mA / cm 2 )]]> Fill factor (%) Energy conversion efficiency (%) Example 1 720.61 36.95 71.40 19.01 Comparative Example 1 726.08 37.01 72.80 19.56 Comparative Example 2 707.95 36.02 59.76 15.24

Claims

1. A method for recycling and processing crystalline silicon perovskite tandem solar cells, characterized in that, Including the following steps: (1) Provide a packaged series battery, wherein the packaged series battery comprises, from bottom to top, a silicon bottom battery, an organic hole transport layer, a perovskite absorber layer, an electron transport layer, a top electrode and a packaged glass, and the packaged glass is first removed from the packaged series battery by heat treatment to obtain an unpackaged series battery. (2) Then the unencapsulated series battery is immersed in an organic solvent at room temperature. After the organic hole transport layer dissolves, the perovskite absorber layer naturally detaches from the silicon bottom battery and floats in the organic solvent, thus obtaining the silicon bottom battery. (3) The separated silicon bottom battery is rinsed with solvent more than twice, and then the silicon bottom battery is transferred to a hot plate for heating and annealing; The organic solvent in step (2) is chlorobenzene (CB).

2. The method for recycling and processing crystalline silicon perovskite tandem solar cells according to claim 1, characterized in that, The equipment used for heat treatment in step (1) includes a heating table, an oven or a hot air gun, with a heat treatment temperature range of 180°C and a heat treatment time range of 10 min.

3. The method for recycling and processing a crystalline silicon perovskite tandem solar cell according to claim 1, characterized in that, The organic hole transport layer is composed of at least one of the following materials: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD).

4. The method for recycling and processing a crystalline silicon perovskite tandem solar cell according to claim 1, characterized in that, In step (3), the solvent is chlorobenzene, the heating annealing temperature is 150°C, and the heating annealing time is 10 min.

5. A battery, characterized in that, From bottom to top, it includes: a silicon bottom cell, a top electrode, and an encapsulation glass; the silicon bottom cell is obtained by the recycling method of the crystalline silicon perovskite tandem solar cell according to any one of claims 1 to 4.

6. A battery according to claim 5, characterized in that, The silicon-based solar cell includes: a bottom electrode, a transparent electrode layer, a P-type substrate doped layer, a substrate passivation layer, a silicon substrate, a substrate surface passivation layer, and an N-type substrate doped layer.

7. A battery according to any one of claims 5 to 6, characterized in that, The silicon bottom cell and the top electrode also include an organic hole transport layer, a perovskite absorber layer, and an electron transport layer, forming a crystalline silicon perovskite tandem solar cell structure.

8. A battery according to claim 7, characterized in that, The organic hole transport layer is composed of at least one of the following materials: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (Meo-2PACz), 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), poly-3-hexylthiophene (P3HT), and 2,2",7,7"-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-oMeTAD).

9. A battery according to claim 7, characterized in that, An inorganic hole transport layer is disposed between the silicon-based solar cell and the organic hole transport layer. The inorganic hole transport layer is nickel oxide (NiO). x ), molybdenum oxide (MoO) x It consists of at least one of cuprous iodide (CuI) and cuprous thiocyanate (CuSCN).

10. A battery according to claim 7, characterized in that, The perovskite absorber layer has an ABX3 structure, with an organic cation at the A site, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + CH3CH2NH3 + or Cs + At least one of them; the B site is a metal cation, including Pb 2+ Sn 2+ At least one of them; the X-position is a halide anion, including F - Cl - ,Br - I - At least one of them.

11. A battery according to claim 7, characterized in that, The electron transport layer is composed of zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide (TiO2), and [6,6]-phenyl C61-butyrate methyl ester (PC). 61 BM), C 60 At least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

12. A battery according to claim 7, characterized in that, The top electrode is at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon (C).

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