Stable four-terminal perovskite-crystalline silicon laminated battery assembly and method

Abstract

The invention discloses a stable four-terminal perovskite-crystalline silicon laminated battery assembly and a method, and belongs to the technical field of photovoltaic device manufacturing. A plurality of diodes packaged by adopting a high-heat-dissipation packaging material are introduced into the structure of the crystalline silicon cell string, so that the blocked crystalline silicon cells can be quickly cooled, and the phenomenon of local overheating is reduced. Meanwhile, a thermoelectric device string with a reversible phase change heat absorption layer is arranged on the back face of the crystalline silicon cell string and is finally connected with the crystalline silicon cell string in parallel. The reversible phase change heat absorption layer can generate phase change when the solar cell works to absorb heat generated by the cell, so that a temperature gradient is generated at the hot end and the cold end of the thermoelectric device; and in a non-working state, the overall temperature of the thermoelectric device is reduced, and the solid paraffin material in the reversible phase change heat absorption layer is subjected to reverse phase change, so that the long-term working stability of the bottom crystalline silicon battery and the conversion efficiency of the four-terminal laminated battery are improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of photovoltaic device manufacturing, and particularly relates to a stable four-terminal perovskite-crystalline silicon laminated battery assembly and method. BACKGROUND

[0002] Since Japanese scientist Akimitsu Kimura manufactured the first perovskite solar cell in 2009, the efficiency of perovskite solar cells has rapidly increased from the initial 3.9% to the certified efficiency of 26.7%. Perovskite materials have excellent photoelectric performance, and their preparation process has a lower temperature, which has the advantages of low energy consumption and low cost for commercialization. However, perovskite solar cells are relatively limited in utilizing the infrared light energy in the solar spectrum, and a large amount of heat energy is generated during operation, which has a certain impact on the performance of the assembly. In order to improve the efficiency and stability of perovskite solar cells, research in recent years has begun to explore the integration of perovskite solar cells with other types of solar cells, such as crystalline silicon cells, into a laminated structure. The four-terminal laminated assembly has one junction box for each of the perovskite and crystalline silicon cells, which are connected to the corresponding circuit for grid connection. In the case of constantly changing outdoor light intensity, the bottom crystalline silicon cell is prone to power surges or is affected after being shaded, resulting in heating of the assembly and a decrease in power. SUMMARY

[0003] The present application aims to overcome the defects in the prior art and provide a stable four-terminal perovskite-crystalline silicon laminated battery assembly and method.

[0004] The specific technical solutions adopted by the present application are as follows: In a first aspect, the present application provides a stable four-terminal perovskite-crystalline silicon laminated battery assembly, comprising a semi-transparent perovskite assembly, a crystalline silicon cell string, and a thermoelectric device arranged between a front plate glass and a back plate glass. The crystalline silicon cell string comprises a plurality of crystalline silicon cell pieces connected in series in the plane, and a high-heat-dissipation diode is connected in series between adjacent crystalline silicon cell pieces and between the crystalline silicon cell pieces and the positive and negative electrodes. Each diode is encapsulated by modified silicone containing high-heat-conducting fillers. Each crystalline silicon cell piece has a thermoelectric device on the back surface, and all the thermoelectric devices are connected in series to form a thermoelectric device string connected in parallel with the crystalline silicon cell string. The hot end of the thermoelectric device faces the back plate glass, and the cold end of the thermoelectric device has a reversible phase-change heat-absorbing layer in contact with the crystalline silicon cell piece.

[0005] Preferably, a film of adhesive is applied between the back plate glass and the thermoelectric device, and between the semi-transparent perovskite assembly and the crystalline silicon cell string.

[0006] Preferably, the high-heat-conducting fillers include expandable graphite, aluminum nitride, and aluminum oxide.

[0007] Preferably, the preparation method of the translucent perovskite component is as follows: S11: The transparent conductive glass is pretreated by washing, drying and disinfection; S12: Prepare the first transport layer on the pretreated transparent conductive glass; S13: Prepare a perovskite layer above the electron transport layer or hole transport layer; S14: Prepare a second transport layer above the perovskite layer; S15: Prepare a transparent metal oxide layer above the second transport layer; The first transport layer is a hole transport layer and the second transport layer is an electron transport layer, or the first transport layer is an electron transport layer and the second transport layer is a hole transport layer.

[0008] Furthermore, the first transport layer comprises SnO2, TiO2, ZnO, AZO, and NiO. x The second transport layer is one or more of the following: metal oxides, including PTAA, 2PACz, and MeO-2PACz; and the second transport layer is Spiro-OMeTAD, P3HT, or C. 60 PC 61 One or more of BM.

[0009] Furthermore, the general structural formula of the perovskite layer material is Cs. x MA y FA 1-x-y Pb(I a Br 1-a )3, with a thickness of 200-800 nm, and prepared by one of the following methods: one-step solution method, two-step solution method, or vapor deposition method; the material of the transparent metal oxide layer is ITO or AZO, with a thickness of 60-150 nm.

[0010] Preferably, the diode is a Schottky diode, which is connected in series with a crystalline silicon solar cell to form a series structure; the method for encapsulating the diode with modified silicone is as follows: Polydimethylsiloxane, mercaptomethylpolysiloxane, dimethyl benzoate, expandable graphite, aluminum nitride, and aluminum oxide powders were uniformly mixed in a mass ratio of 10:5:0.5:1:2:0.5 and uniformly sprayed onto the soldered diode to a thickness >2 mm. Subsequently, the mixture was irradiated under UV-395 nm at a curing energy of 1000 mJ / cm². 2 This forms a high-heat-dissipation diode.

[0011] Preferably, the thermoelectric device includes a reversible phase change heat-absorbing layer, a cold end, a first electrode, a P-type column, an N-type column, a second electrode, and a hot end; the reversible phase change heat-absorbing layer is a ceramic or metal shell filled with solid paraffin wax, the phase change temperature of the solid paraffin wax being between 40-60℃; one side of the cold end is in contact with the reversible phase change heat-absorbing layer, and the two ends of the other side are symmetrically provided with the first electrode; a P-type column and an N-type column are respectively provided above the first electrode on both sides, and the second electrode and the hot end are sequentially stacked above the P-type column and the N-type column.

[0012] Furthermore, the hot end material is ceramic or metal, the materials of the first electrode and the second electrode include Ag, Au, Cu, and Al, the P-type pillar material is bismuth telluride alloy or silicon nanowire, and the N-type pillar material includes lead telluride alloy, tin selenide alloy, and copper selenide alloy; the thickness of the thermoelectric device is 0.2-2 mm.

[0013] Secondly, the present invention provides a method for using the stable four-terminal perovskite-crystalline silicon tandem solar cell module described in the first aspect, as follows: In operation, the hot end of the thermoelectric device absorbs infrared radiation heat energy from sunlight and heat energy generated by the semi-transparent perovskite module and crystalline silicon cell string; the solid paraffin in the reversible phase change heat absorption layer reaches the phase change temperature, undergoes a solid-to-liquid phase transformation, and absorbs heat during the melting process, thereby lowering the temperature of the cold end and creating a temperature gradient between the hot and cold ends; under the temperature gradient, electrons and charge carriers in the P-type and N-type pillars diffuse downwards respectively, thereby generating a potential difference between the first electrodes and completing the power generation; When not in operation, the overall temperature of the thermoelectric device decreases, and the solid paraffin in the reversible phase change heat absorption layer undergoes a reverse phase change, so that it can continue to undergo phase change heat absorption when it is in operation again. This helps the thermoelectric device to continuously convert the heat energy that was not absorbed by the crystalline silicon solar cell or generated by the crystalline silicon solar cell into electrical energy when it is in operation, thereby reducing the operating temperature and improving the long-term working stability of the crystalline silicon solar cell and the conversion efficiency of the tandem solar cell module. In addition, the diodes connected in series in the crystalline silicon cell string can quickly cool down the shaded crystalline silicon cells and reduce local overheating.

[0014] Compared with the prior art, the present invention has the following advantages: 1) Improve component stability and security By introducing a high-heat-dissipation diode between the crystalline silicon solar cell and the series circuit, localized overheating (hot spot effect) is avoided due to shading or uneven power distribution. Modified high-thermal-conductivity silicone encapsulation reduces the diode peak temperature from 60-66℃ to approximately 36℃, and the diode thermal runaway efficiency to 4.2%, effectively improving the long-term operational reliability of the crystalline silicon solar cell string.

[0015] 2) Achieve efficient thermal management A series of thermoelectric devices are arranged on the back of a crystalline silicon solar cell, with the cold end in close contact with a reversible phase change heat-absorbing layer. Solid paraffin undergoes a phase change and absorbs heat within the range of 40-60℃, which can significantly reduce the operating temperature of the cell. At the same time, the temperature difference between the hot and cold ends drives the thermoelectric devices to generate additional electrical work, further improving energy utilization efficiency.

[0016] 3) Significantly improves photoelectric conversion efficiency The results of the embodiments show that the efficiency of the four-terminal perovskite-crystalline silicon-thermoelectric tandem module of the present invention reaches 27.2%-27.3%, which is a significant improvement compared with the efficiency of standalone perovskite modules (approximately 16%) or standalone crystalline silicon modules (approximately 19%). The average output power measured outdoors over 12 months is 287W, which is about 14%-15% higher than that of conventional standard process tandem modules (250W).

[0017] 4) Enhance long-term reliability and environmental adaptability Reversible phase change materials can achieve multiple cycles of heat absorption and release during day and night / seasonal alternation, alleviating the stress and efficiency degradation of crystalline silicon cells caused by sudden temperature rises; combined with diode heat dissipation and thermoelectric power generation, the module can still maintain high power stability under outdoor high-intensity sunlight and partial shading conditions (power retention rate of 94.2%, significantly better than the comparative ratio of 83.5%-88.0%). Attached Figure Description

[0018] Figure 1 It is a thermoelectric device structure with a reversible phase change heat absorption layer; Figure 2 This is a schematic diagram of the structure of the four-terminal perovskite-crystalline silicon tandem solar cell module of the present invention; Figure 3 This is a schematic diagram of the connection structure of a crystalline silicon cell string, diodes, and thermoelectric devices. Figure 4 This study compares the output power of the tandem solar cell module (i.e., perovskite-silicon-thermoelectric tandem solar cell) of the present invention with that of a standard tandem solar cell module (i.e., perovskite solar cell) in the prior art during a 12-month outdoor operation period.

[0019] The figures are labeled as follows: 1 is the reversible phase change endothermic layer, 2 is the cold end, 3 is the first electrode, 4 is the P-type column, 5 is the N-type column, 6 is the second electrode, 7 is the hot end, and 8 is solid paraffin. Detailed Implementation

[0020] The present invention will be further described and illustrated below with reference to the accompanying drawings and specific embodiments. The technical features of each embodiment of the present invention can be combined accordingly, provided that there is no mutual conflict.

[0021] This invention provides a stable four-terminal perovskite-crystalline silicon tandem solar cell module. By introducing multiple diodes encapsulated with high-heat-dissipation packaging materials into the crystalline silicon cell string structure, and connecting the diodes in series with the crystalline silicon cells, the high-heat-dissipation packaging of the diodes can quickly cool down the shaded crystalline silicon cells, reducing localized overheating. Simultaneously, a string of thermoelectric devices with a reversible phase-change heat-absorbing layer is arranged on the back of the crystalline silicon cell string, ultimately connected in parallel with the crystalline silicon cell string to form a positive and a negative terminal. The reversible phase-change heat-absorbing layer on the back of the thermoelectric device can undergo a phase change to absorb the heat generated by the solar cell (including semi-transparent perovskite modules and crystalline silicon cell strings) during operation, creating a temperature gradient between the hot and cold ends of the thermoelectric device. In the non-operating state, the overall temperature of the thermoelectric device decreases, and the solid paraffin material in the reversible phase-change heat-absorbing layer undergoes a reverse phase change, allowing it to continue absorbing heat during the next operation. This enables the thermoelectric device to continuously convert heat energy not absorbed by the crystalline silicon cells or generated during battery operation into electrical energy during operation, reducing the operating temperature and thus improving the long-term operating stability of the bottom crystalline silicon cell and the conversion efficiency of the four-terminal stacked cell. This invention also proposes the concept of "packaging-level thermal management," which involves introducing a highly thermally conductive modified silicone material during diode packaging. This material not only ensures the electrical connection stability of the diode but also rapidly guides and diffuses heat within the crystalline silicon series structure under conditions of localized overheating caused by high-intensity outdoor sunlight and shading, suppressing the "hot spot effect." The modified silicone material mentioned above incorporates high thermal conductivity fillers (such as expandable graphite, aluminum nitride, and aluminum oxide), which achieve low-temperature rapid curing under ultraviolet light irradiation, forming an integrated heat dissipation path with the diode, effectively improving the diode's operational reliability and the thermal balance capability of the stacked structure.

[0022] The structure and method of the stacked battery assembly of the present invention will be described in detail below.

[0023] In this invention, the tandem battery module mainly includes a semi-transparent perovskite module, a crystalline silicon cell string, and thermoelectric devices disposed between the front glass and the back glass, such as... Figure 2 As shown.

[0024] In a preferred embodiment of the present invention, an adhesive film is applied between the backplate glass and the thermoelectric device, and an adhesive film is applied between the semi-transparent perovskite module and the crystalline silicon cell string.

[0025] As a preferred embodiment of the present invention, the method for preparing a semi-transparent perovskite module is as follows: S11: The transparent conductive glass is pretreated by washing, drying and disinfection.

[0026] In actual use, the steps are as follows: The transparent conductive glass was ultrasonically cleaned sequentially with cleaning solution, deionized water, ethanol, and isopropanol. The cleaned transparent conductive glass was then dried with an N2 gun and treated with UV-O3 for 10 minutes.

[0027] S12: Prepare the first transport layer on the pretreated transparent conductive glass.

[0028] S13: Prepare a perovskite layer above the electron transport layer or hole transport layer.

[0029] In practical applications, the general structural formula of perovskite layer materials is Cs. x MA y FA 1-x-y Pb(I a Br 1-a )3, with a thickness of 200-800nm, and the preparation process can be one of the following: one-step solution method, two-step solution method, or vapor deposition method.

[0030] S14: Prepare a second transport layer on top of the perovskite layer.

[0031] In practical applications, when the first transport layer is a hole transport layer, the second transport layer should be an electron transport layer; conversely, when the first transport layer is an electron transport layer, the second transport layer should be a hole transport layer. Adjustments can be made based on specific circumstances. The material of the first transport layer includes metal oxides (e.g., SnO2, TiO2, ZnO, AZO, NiO). x The second transport layer is one or more of the following: (etc.) or organic materials (e.g., PTAA, 2PACz, MeO-2PACz), and the second transport layer is Spiro-OMeTAD, P3HT, C 60 PC 61 One or more of BM.

[0032] S15: Prepare a transparent metal oxide layer above the second transport layer.

[0033] In practical applications, the transparent metal oxide layer can be made of ITO or AZO, with a thickness of 60-150 nm.

[0034] In this invention, the crystalline silicon solar cell string comprises multiple crystalline silicon solar cells connected in series in the same plane. High heat dissipation diodes are connected in series between adjacent crystalline silicon solar cells and between the crystalline silicon solar cells and the positive and negative electrodes. Each diode is encapsulated with modified silicone containing highly thermally conductive filler.

[0035] As a preferred embodiment of the present invention, such as Figure 3 As shown, the tandem crystalline silicon solar cells have a serpentine structure.

[0036] In a preferred embodiment of the present invention, the diode can be a high-heat-dissipation Schottky diode. After the bottom crystalline silicon solar cell is fabricated, it is connected in series with the crystalline silicon solar cell to form a series structure, with a diode added in the middle of each solar cell. Subsequently, modified silicone is used for encapsulation during the diode encapsulation process. Encapsulating the diode in modified silicone can achieve heat dissipation. The modified silicone contains fillers with high thermal conductivity, such as expandable graphite, aluminum nitride, and aluminum oxide. This modified silicone has excellent thermal conductivity (approximately 600 W / mK), which can effectively dissipate the heat accumulated around the diode, prevent thermal breakdown of the diode, and stabilize its switching behavior. The method of encapsulating the diode with modified silicone is as follows: Polydimethylsiloxane, mercaptomethylpolysiloxane, dimethyl benzoate, expandable graphite, aluminum nitride, and alumina powders were uniformly mixed in a mass ratio of 10:5:0.5:1:2:0.5. The mixture was then uniformly sprayed onto the soldered diode using a spraying device to a thickness >2 mm. Subsequently, it was irradiated under UV-395 nm at a curing energy of 1000 mJ / cm². 2 This forms a high heat dissipation diode, ensuring a dense package structure and a continuous heat conduction path.

[0037] In this invention, each crystalline silicon solar cell has a thermoelectric device on its back side. All thermoelectric devices are connected in series to form a thermoelectric device string connected in parallel with the crystalline silicon solar cell string. The hot end of the thermoelectric device faces the back glass and can absorb infrared radiation heat energy and heat energy generated by the bottom crystalline silicon solar cell. The cold end of the thermoelectric device has a reversible phase change heat absorption layer, which is in contact with the crystalline silicon solar cell.

[0038] Under operating conditions, the solid paraffin in the reversible phase change endothermic layer undergoes a solid-to-liquid phase transition as its temperature reaches the phase change temperature. During this melting process, it absorbs heat, thereby lowering the temperature at the cold end and creating a temperature gradient between the hot and cold ends. Under this temperature gradient, electrons and charge carriers in the P-type and N-type pillars diffuse downwards, generating a potential difference between the electrodes and thus producing electricity.

[0039] As a preferred embodiment of the present invention, such as Figure 1 As shown, the thermoelectric device mainly includes a reversible phase change heat-absorbing layer 1, a cold end 2, a first electrode 3, a P-type pillar 4, an N-type pillar 5, a second electrode 6, and a hot end 7. The reversible phase change heat-absorbing layer 1 is a ceramic or metal shell filled with solid paraffin wax 8, the phase change temperature of which is between 40-60℃. One side of the cold end 2 is in contact with the reversible phase change heat-absorbing layer 1, and the two ends of the other side are symmetrically provided with the first electrode 3. The P-type pillar 4 and the N-type pillar 5 are respectively provided above the first electrode 3 on both sides, and the second electrode 6 and the hot end 7 are stacked sequentially above the P-type pillar 4 and the N-type pillar 5.

[0040] In a preferred embodiment of the present invention, the hot end 7 can be made of ceramic or metal with good thermal conductivity. The reversible phase change heat absorption layer is composed of a hollow ceramic or metal with good thermal conductivity, and the hollow area in the middle is filled with solid paraffin with a phase change temperature of 40-60℃. The materials of the first electrode 3 and the second electrode 6 can be metals with excellent electrical conductivity such as Ag, Au, Cu, and Al. The P-type pillar 4 can be made of bismuth telluride (Bi2Te3) alloy or silicon nanowires, and the N-type pillar can be made of lead telluride (PbTe) alloy, tin selenide (SnSe) alloy, or copper selenide (Cu2Se) alloy. The thickness of the thermoelectric device is 0.2-2 mm. In practical use, the thermoelectric device drives the diffusion of electrons and charge carriers through a temperature gradient to generate a potential difference to generate electricity.

[0041] The method for using the stable four-terminal perovskite-crystalline silicon tandem solar cell module described above is as follows: In operation, the hot end 7 of the thermoelectric device absorbs infrared radiation heat energy from sunlight, as well as heat energy generated by the semi-transparent perovskite module and crystalline silicon cell string. The solid paraffin 8 in the reversible phase change heat-absorbing layer 1 reaches its phase change temperature, undergoing a solid-to-liquid phase transition and absorbing heat during melting, thus lowering the temperature of the cold end 2 and creating a temperature gradient between the hot end 7 and the cold end 2. Under this temperature gradient, electrons and charge carriers in the P-type pillar 4 and N-type pillar 5 diffuse downwards, generating a potential difference between the first electrodes 3, thus completing power generation.

[0042] In the non-operating state, the overall temperature of the thermoelectric device decreases, and the solid paraffin 8 in the reversible phase change heat absorption layer 1 undergoes a reverse phase change, so that it can continue to undergo phase change heat absorption when it is working again. This helps the thermoelectric device to continuously convert the heat energy that was not absorbed by the crystalline silicon solar cell or generated by the crystalline silicon solar cell into electrical energy when it is in operation, thereby reducing the operating temperature and improving the long-term working stability of the crystalline silicon solar cell and the conversion efficiency of the tandem solar cell module.

[0043] In addition, the diodes connected in series in the crystalline silicon cell string can quickly cool down the shaded crystalline silicon cells and reduce local overheating.

[0044] The following examples will illustrate the stacked battery assembly and its effects according to the present invention.

[0045] Example 1 This embodiment fabricates a stable four-terminal perovskite-crystalline silicon tandem solar cell module. The specific fabrication method is as follows: S1: Fabrication of the top translucent perovskite assembly S11, Pretreatment of transparent conductive glass: The FTO substrate (i.e., transparent conductive glass) with a size of 30 cm*40 cm is ultrasonically cleaned with deionized water, isopropanol and acetone in sequence for 15 min each. Then the FTO substrate is dried with nitrogen and UV treated for 10 min.

[0046] S12, Preparation of the electron transport layer: SnO2 was prepared as an electron transport layer on the pretreated FTO substrate. The SnO2 concentration was 3.3 mg / mL. It was coated on the FTO at a speed of 1000 mm / min and then transferred to a hot plate at 160℃ for annealing for 15 min.

[0047] S13, Preparation of the perovskite layer: Dissolve 30 mmol of PbBr2 (1 mmol) in 30 ml of a mixed solvent of DMF:NMP = 4:1 (v / v), heat and stir at 60 °C for 2 h to obtain a PbBr2 precursor solution. Take 1.5 ml of the PbBr2 precursor solution and coat it onto the electron transport layer at a speed of 800 mm / min. After coating, anneal the substrate at 120 °C for 10 min to obtain a PbBr2 film. Take 1.5 ml of FAI IPA solution and coat it onto the PbBr2 film at a speed of 800 mm / min, then place it on a hot table at 150 °C for annealing for 10 min to obtain a dense perovskite light-absorbing layer.

[0048] S14, Preparation of the hole transport layer: Spiro-OMeTAD was dissolved in chlorobenzene at a concentration of 80 mg / mL. A 1M Li-TFSI acetonitrile solution and TBP were added as additives at concentrations of 35 μL / mL and 15 μL / mL, respectively. After stirring for 1 h, the mixture was coated onto a perovskite layer. After completion, the layer was placed in a light-protected air-drying oven for 10 h to obtain the hole transport layer.

[0049] S15, Preparation of transparent metal oxide layer: The battery with the hole transport layer prepared is placed in a magnetron sputtering device, and 120 nm ITO is deposited as a transparent electrode (i.e., transparent metal oxide layer) under a vacuum of 4E-3 Pa.

[0050] S2: Fabrication of thermoelectric cells (i.e., thermoelectric devices) Ag was deposited as electrodes on two alumina ceramic plates, with one plate serving as the cold-end electrode and the electrodes divided using a mask during deposition. The deposition vacuum was 4E-4 Pa, and the thickness was 120 nm. Bi₂Te₃ (P-type pillars) and PbTe (N-type pillars) were then welded onto the electrodes. Finally, a ceramic interlayer with good thermal conductivity at its upper end was welded onto the back of the cold end as a reversible phase transition absorption layer. The ceramic interlayer was filled with solid paraffin, primarily composed of n-octadecane.

[0051] S3: Fabrication of crystalline silicon solar cell strings Each crystalline silicon solar cell is soldered to a high-heat-dissipation diode to form a string. After each crystalline silicon solar cell is connected in series with a Schottky diode, it is encapsulated using modified high thermal conductivity silicone. This silicone is formulated with the following components: 10g polydimethylsiloxane, 5g mercaptomethyl polysiloxane, 0.5g benzoin dimethyl ether (photoinitiator), 1g expandable graphite, 2g aluminum nitride, and 0.5g alumina powder. After uniformly mixing the above components, the mixture is applied to the surface of the soldered diode using a spraying device, with an encapsulation thickness >2 mm. Subsequently, it is irradiated at a wavelength of 395 nm with a curing energy of 1000 mJ / cm². 2 This forms a dense, continuous, and highly thermally conductive encapsulation layer. This layer structure can significantly suppress overheating problems in diodes caused by shielding or changes in operating current during actual operation.

[0052] To verify the thermal control performance of the modified high thermal conductivity silicone encapsulation, three parallel sample groups were set up in this embodiment, as shown in Table 1.

[0053] Table 1 S4, Assemble a four-terminal stacked structure: An adhesive film is applied to the back glass, and thermoelectric devices, crystalline silicon cell strings, and the adhesive film are then applied on top of it, ultimately forming a four-terminal perovskite-crystalline silicon tandem cell module.

[0054] To verify the effectiveness of the tandem solar cell module (i.e., perovskite-silicon-thermoelectric tandem solar cell-1) prepared in this embodiment, its cell efficiency was compared with that of perovskite solar cell-1, silicon solar cell-1, silicon solar cell-1 after being filtered by perovskite top cell, and crystalline silicon bottom thermoelectric cell-1, as shown in Table 2.

[0055] The fabrication steps of the perovskite solar cell-1 are basically the same as those in Example S1, but it is not stacked with crystalline silicon / thermoelectric devices; only the performance of a single cell is tested. Silicon solar cell-1: Commercially available crystalline silicon cells (one-stage D-Matrix crystalline silicon cells) are used, without heating devices or diode encapsulation; it serves only as a single-junction control. Silicon solar cell-1 after perovskite top cell filtering: A layer of perovskite top cell filter glass is covered on the monocrystalline silicon cell (but without electrical coupling) to simulate the bottom cell response under spectral separation conditions. Crystalline silicon bottom thermoelectric cell-1: Thermoelectric devices are directly attached to the back of the monocrystalline silicon cell, but a phase change heat absorption layer and diode heat dissipation encapsulation are not used.

[0056] Table 2 The data above shows that the photoelectric conversion efficiency of the perovskite solar cell-1 is 16.07%, and that of the silicon solar cell-1 is 19.10%. When the silicon cell is under the filtering condition of the perovskite top cell, its efficiency drops to 9.05%. The efficiency of the standalone crystalline silicon bottom thermoelectric cell-1 is even lower, at only 2.10%. In contrast, the perovskite-silicon-thermoelectric tandem solar cell-1 prepared in this embodiment achieves a comprehensive efficiency of 27.23%, significantly higher than that of single-junction cells and simple stacked combinations. This result demonstrates that the tandem structure proposed in this invention can effectively utilize the energy after spectral separation, and through the synergistic effect of the thermoelectric device and the phase change heat absorption layer, it both reduces the temperature rise of the module and supplements the electrical output, thus achieving a comprehensive efficiency significantly superior to that of individual cells.

[0057] Furthermore, the output power of the tandem solar cell module (i.e., perovskite-silicon-thermoelectric tandem solar cell) prepared in this embodiment was compared with that of the perovskite solar cell after 12 months of outdoor operation. The results are as follows: Figure 4 As shown in the figure, the average output power of the tandem solar cell obtained in this embodiment is 287 W, which is 37 W higher than that of the standard process tandem solar cell module (perovskite solar cell, 250 W), further verifying that the structure of the present invention has higher output power and stability during long-term outdoor operation.

[0058] Example 2 This embodiment fabricates a stable four-terminal perovskite-crystalline silicon tandem solar cell module. The specific fabrication method is as follows: S1: Fabrication of the top translucent perovskite assembly A 30*40 cm FTO (fluorine-doped tin oxide) substrate was sequentially ultrasonically cleaned with deionized water, isopropanol, and acetone for 15 min each. The FTO substrate was then dried with nitrogen and UV-treated for 10 min. NiO was then prepared on the FTO conductive glass. x As a hole transport layer, NiO xThe concentration was 20 mg / mL. After being coated onto FTO, the solution was transferred to a hot plate at 160 °C and annealed for 15 min. Preparation of the perovskite layer: Perovskite precursor solution preparation: Weigh 114.0 mg MABr, 387.0 mg PbBr2, 450.0 mg MACl, 675.0.5 mg CsI, 8310.0 mg FAI, and 21600.0 mg PbI2, and dissolve them in 30 mL of a mixed solvent of DMF:DMSO (4:1, v / v). 3 mL of the perovskite precursor solution was coated onto FTO glass at a speed of 1000 mm / min. After coating, 4.8 mL of CB antisolvent was coated, and then the solution was transferred to a hot plate at 120 °C and annealed for 20 min to obtain the perovskite layer. Fabrication of the electron transport layer: The prepared perovskite thin film was transferred to a thermal evaporation apparatus, where 30 nm of C60 and 8 nm of BCP were deposited under a vacuum of 3E-4 MPa. This yielded the electron transport layer. Fabrication of the transparent electrode: The battery with the prepared hole transport layer was placed in a magnetron sputtering apparatus, where 100 nm of AZO was deposited as the transparent electrode under a vacuum of 4E-3 Pa.

[0059] S2: Fabrication of thermoelectric cells (i.e., thermoelectric devices) Ag was deposited as electrodes on two alumina ceramic plates, with one plate serving as the cold-end electrode and the electrodes divided using a mask during deposition. The deposition vacuum was 4E-4 Pa, and the thickness was 120 nm. Silicon nanowires, serving as P-type pillars, and PbTe, serving as N-type pillars, were then welded onto the electrodes. Finally, a ceramic interlayer with good thermal conductivity at its upper end was welded to the back of the cold end as a reversible phase transition absorption layer, filled with solid paraffin primarily composed of n-tetracosane and n-octadecane.

[0060] S3: Fabrication of crystalline silicon solar cell strings Each crystalline silicon solar cell is soldered to a high-heat-dissipation diode to form a string. After each crystalline silicon solar cell is connected in series with a Schottky diode, it is encapsulated using modified high thermal conductivity silicone. This silicone is formulated with the following components: 10g polydimethylsiloxane, 5g mercaptomethyl polysiloxane, 0.5g benzoin dimethyl ether (photoinitiator), 1g expandable graphite, 2g aluminum nitride, and 0.5g alumina powder. After uniformly mixing the above components, the mixture is applied to the surface of the soldered diode using a spraying device, with an encapsulation thickness >2 mm. Subsequently, it is irradiated at a wavelength of 395 nm with a curing energy of 1000 mJ / cm². 2 This forms a dense, continuous, and highly thermally conductive encapsulation layer. This layer structure can significantly suppress overheating problems in diodes caused by shielding or changes in operating current during actual operation.

[0061] To evaluate the operational reliability of the components under different silicone structures, this embodiment sets up three structures and simulates outdoor sunlight for 12 months of long-term operation. The results are shown in Table 3.

[0062] Table 3 The results further verified that the thermal conductivity of diode packaging is directly related to the operational stability of the entire crystalline silicon module, and that high thermal conductivity modified silicone can effectively control the accumulation of local heat sources and alleviate structural stress aging.

[0063] S4, Assemble a four-terminal stacked structure: An adhesive film is applied to the back glass, and thermoelectric devices, crystalline silicon cell strings, and the adhesive film are then applied on top of it, ultimately forming a four-terminal perovskite-crystalline silicon tandem cell module.

[0064] To verify the effectiveness of the tandem solar cell module (i.e., perovskite-silicon-thermoelectric tandem solar cell-2) prepared in this embodiment, its cell efficiency was compared with that of perovskite solar cell-2, silicon solar cell-2, silicon solar cell-2 after being filtered by perovskite top cell, and crystalline silicon bottom thermoelectric cell-2, as shown in Table 4.

[0065] Among them, "Perovskite Solar Cell-2" and "Crystal Silicon Bottom Thermoelectric Cell-2" were both fabricated in-house, while "Silicon Solar Cell-2" was a commercially available cell slice (a general procurement information template is provided), as detailed below: Differences in sample source and preparation: 1. Perovskite Solar Cell-2 (Homemade) This sample is a single-junction perovskite solar cell, fabricated using process S1 in Example 2 (FTO / NiOx / perovskite light-absorbing layer / C60 / BCP / AZO transparent electrode). It differs from the stacked assembly of this invention in that it does not contain any crystalline silicon base cell, thermoelectric devices, or phase-change heat-absorbing layer, nor does it include diode packaging or parallel branches; it is only used to provide a baseline performance for single-junction comparison.

[0066] 2. Silicon solar cell-2 (commercial purchase) The samples were commercially available monocrystalline PERC solar cells, with the following specifications: 156 mm in size, 190 μm in thickness, 5-9 BB of grid lines, and a nominal cell efficiency of ≥19% (indoor testing standard AM1.5G). In the experiment, the entire cell was cut into smaller test pieces of equal area. No thermoelectric / phase-change / diode packaging treatments related to this invention were performed; the cells were used solely as a silicon single-junction control.

[0067] Supply channels: One-way D-Matrix crystalline silicon solar cell, conversion efficiency 19.28%.

[0068] 3. Silicon solar cell after filtering by perovskite top cell - 2 (derived control) This control is not an independently purchased sample, but rather a filter layer / top cell glass with an equivalent spectrum to the perovskite top cell in Example 2 is covered on the surface of "Silicon Solar Cell-2" (without electrical coupling) to simulate spectral separation in a four-terminal stack; only the incident spectral conditions are changed, without altering the silicon cell structure and packaging, to evaluate the impact of spectral filtering on the bottom cell output.

[0069] 4. Crystalline silicon bottom thermoelectric cell-2 (homemade) This sample was obtained by mounting thermoelectric devices on the back of a "silicon solar cell-2". The thermoelectric devices were fabricated according to process S2 in Example 2. However, it differs from the present invention in that: a reversible phase change heat absorption layer was not provided, it was not connected in parallel with the crystalline silicon string to form a "thermoelectric device string", and no parallel protection diodes and high thermal conductivity packages were applied to the crystalline silicon sub-string terminals; therefore, it is only used to evaluate the control effect of "only heating the thermoelectric device, no phase change / no protection diode / no parallel coupling".

[0070] 5. Perovskite-silicon-thermoelectric tandem solar cell - 2 (self-made, sample of this invention) Prepared according to steps S1-S4 of Example 2, comprising: a semi-transparent perovskite top cell, a commercially available silicon bottom cell string, a back thermoelectric device string, and a reversible phase change heat absorption layer; a protection diode parallel branch is provided at the crystalline silicon sub-string end and encapsulated with high thermal conductivity modified silicone; and four terminals are led out respectively.

[0071] Table 4 Note 1: "Silicon Solar Cell-2" is a cut sample of a commercially available monocrystalline PERC cell; the others marked "Homemade / Derived Control" were all prepared in our laboratory according to the corresponding steps.

[0072] Note 2: "Silicon solar cell-2 after perovskite top cell filtration" refers to the test conditions under which an equivalent spectral filter is applied to "Silicon solar cell-2" without changing its structure.

[0073] Note 3: "Crystal Silicon Bottom Thermoelectric Cell-2" does not include the phase change layer and protection diode package, and is only used for thermoelectric mounting comparison.

[0074] The data above shows that, under the same illumination conditions (AM1.5G, 100 mW / cm²), single-junction and tandem solar cells exhibit performance comparable to each other. 2 The output parameters are as follows: the open-circuit voltage (VOC) of the perovskite solar cell-2 is 1.06 V, and the short-circuit current density (JSC) is 19.5 mA / cm². 2 The fill factor (FF) is 77.3%, and the photoelectric conversion efficiency (PCE) is 15.98%; the PCE of silicon solar cell-2 is 19.28%.

[0075] When the silicon cell is subjected to the filtering conditions of a perovskite top cell, its JSC drops to 18.3 mA / cm². 2 The efficiency dropped to 9.08%, indicating that the top perovskite layer absorbed the visible light energy, leaving only infrared light to reach the bottom cell. When thermoelectric devices are mounted on the back of the silicon cell alone (without phase change layer and diode packaging), the heat loss is significant, with a PCE of only 2.16%.

[0076] In comparison, the perovskite-silicon-thermoelectric tandem solar cell-2 fabricated in this invention achieves an overall efficiency of 27.22%, significantly higher than any single-junction or simple stacked structure. Its improved overall performance mainly stems from: (1) The thermoelectric device and the reversible phase change heat absorption layer work together to effectively reduce the temperature of the crystalline silicon layer by about 10-15℃; (2) High thermal conductivity packaged diodes enable rapid heat dissipation and current bypass under shielding conditions, avoiding hot spot effects; (3) The stacked structure enables spectral zoning absorption and waste heat recovery, improving the efficiency of dual utilization of light and heat energy.

[0077] Therefore, the four-terminal perovskite-silicon-thermoelectric stacked assembly of the present invention is significantly superior to the traditional structure in terms of stability and energy conversion.

[0078] Compared to single-junction silicon solar cells-2 (19.28%) and single-junction perovskite solar cells-2 (15.98%), the photoelectric conversion efficiency of the tandem solar cell of this invention is improved by approximately 41%-70%; compared to the thermoelectric control without phase change / diode packaging (2.16%), the overall system output power is increased by more than 12 times. After 12 months of outdoor testing, the average output power of the tandem module was approximately 287 W, with a power retention rate of 94.2%, significantly better than the comparative example of 83.5%-88.0%. These results verify that the present invention possesses excellent thermal control and photoelectric stability performance during long-term operation.

[0079] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all technical solutions obtained through equivalent substitution or transformation fall within the protection scope of the present invention.

Claims

1. A stable four-terminal perovskite-crystalline silicon tandem solar cell module, characterized in that, This includes a semi-transparent perovskite module, crystalline silicon cell strings, and thermoelectric devices disposed between the front and back glass panels; The crystalline silicon solar cell string comprises several crystalline silicon solar cells connected in series in a plane. High heat dissipation diodes are connected in series between adjacent crystalline silicon solar cells and between the crystalline silicon solar cells and the positive and negative electrodes. Each diode is encapsulated with modified silicone containing high thermal conductivity filler. Each crystalline silicon solar cell has a thermoelectric device on its back side. All thermoelectric devices are connected in series to form a thermoelectric device string in parallel with the crystalline silicon solar cell string. The hot end of the thermoelectric device faces the back glass, and the cold end of the thermoelectric device is provided with a reversible phase change heat absorption layer, which is in contact with the crystalline silicon solar cell.

2. The stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 1, characterized in that, An adhesive film is applied between the backplate glass and the thermoelectric device, and between the semi-transparent perovskite module and the crystalline silicon cell string.

3. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 1, characterized in that, The high thermal conductivity filler includes expandable graphite, aluminum nitride, and aluminum oxide.

4. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 1, characterized in that, The method for preparing the semi-transparent perovskite component is as follows: S11: The transparent conductive glass is pretreated by washing, drying and disinfection; S12: Prepare the first transport layer on the pretreated transparent conductive glass; S13: Prepare a perovskite layer above the electron transport layer or hole transport layer; S14: Prepare a second transport layer above the perovskite layer; S15: Prepare a transparent metal oxide layer above the second transport layer; The first transport layer is a hole transport layer and the second transport layer is an electron transport layer, or the first transport layer is an electron transport layer and the second transport layer is a hole transport layer.

5. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 4, characterized in that, The first transport layer comprises SnO2, TiO2, ZnO, AZO, and NiO. x The second transport layer is one or more of the following: metal oxides, including PTAA, 2PACz, and MeO-2PACz; and the second transport layer is Spiro-OMeTAD, P3HT, or C. 60 PC 61 One or more of BM.

6. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 4, characterized in that, The general structural formula of the perovskite layer material is Cs. x MA y FA 1-x-y Pb(I a Br 1-a )3, with a thickness of 200-800 nm, and prepared by one of the following methods: one-step solution method, two-step solution method, or vapor deposition method; the material of the transparent metal oxide layer is ITO or AZO, with a thickness of 60-150 nm.

7. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 1, characterized in that, The diode is a Schottky diode, which is connected in series with a crystalline silicon solar cell to form a series structure; the method for encapsulating the diode with modified silicone is as follows: Polydimethylsiloxane, mercaptomethylpolysiloxane, dimethyl benzoate, expandable graphite, aluminum nitride, and aluminum oxide powders were uniformly mixed in a mass ratio of 10:5:0.5:1:2:0.5 and uniformly sprayed onto the soldered diode to a thickness >2 mm. Subsequently, the mixture was irradiated under UV-395 nm at a curing energy of 1000 mJ / cm². 2 This forms a high-heat-dissipation diode.

8. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 1, characterized in that, The thermoelectric device includes a reversible phase change heat absorption layer (1), a cold end (2), a first electrode (3), a P-type column (4), an N-type column (5), a second electrode (6), and a hot end (7). The reversible phase change heat absorption layer (1) is a ceramic or metal shell filled with solid paraffin (8), and the phase change temperature of the solid paraffin (8) is between 40-60℃. One side of the cold end (2) is in contact with the reversible phase change heat absorption layer (1), and the two ends of the other side are symmetrically provided with the first electrode (3). The first electrode (3) on both sides is provided with a P-type column (4) and an N-type column (5) respectively, and the second electrode (6) and the hot end (7) are stacked on top of the P-type column (4) and the N-type column (5) in sequence.

9. A stable four-terminal perovskite-crystalline silicon tandem solar cell module according to claim 8, characterized in that, The hot end (7) is made of ceramic or metal. The materials of the first electrode (3) and the second electrode (6) include Ag, Au, Cu, and Al. The material of the P-type column (4) is bismuth telluride alloy or silicon nanowire. The material of the N-type column (5) includes lead telluride alloy, tin selenide alloy, and copper selenide alloy. The thickness of the thermoelectric device is 0.2-2 mm.

10. A method of using the stable four-terminal perovskite-crystalline silicon tandem solar cell module as described in claim 8, characterized in that, Specifically as follows: In operation, the hot end (7) of the thermoelectric device absorbs the infrared radiation heat energy from sunlight and the heat energy generated by the semi-transparent perovskite module and the crystalline silicon battery string; the solid paraffin (8) in the reversible phase change heat absorption layer (1) reaches the phase change temperature, undergoes a solid-to-liquid phase transformation, and absorbs heat during the melting process, thereby reducing the temperature of the cold end (2) and generating a temperature gradient between the hot end (7) and the cold end (2); under the temperature gradient, electrons and charge carriers in the P-type column (4) and N-type column (5) diffuse downwards respectively, thereby generating a potential difference between the first electrode (3) and completing the power generation; In the non-working state, the overall temperature of the thermoelectric device decreases, and the solid paraffin (8) in the reversible phase change heat absorption layer (1) undergoes a reverse phase change, so that it can continue to undergo phase change heat absorption when working again. This helps the thermoelectric device to continuously convert the heat energy that was not absorbed by the crystalline silicon cell or generated by the crystalline silicon cell into electrical energy when working, thereby reducing the working temperature and improving the long-term working stability of the crystalline silicon cell and the conversion efficiency of the tandem cell module. In addition, the diodes connected in series in the crystalline silicon cell string can quickly cool down the shaded crystalline silicon cells and reduce local overheating.

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