A method for recycling lead metal in waste lead-acid batteries to prepare perovskite light-emitting / photovoltaic devices

Abstract

This invention belongs to the field of waste resource recycling and optoelectronic material preparation technology, specifically relating to a method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries. This method focuses on recycling waste lead-acid batteries through a "wet-fire-wet" green process. The disassembled electrode plates undergo desulfurization, calcination, and halogenation processes to recrystallize and obtain lead halides (PbI2 and PbBr2), which are then used as raw materials for preparing high-performance perovskite light-emitting / photovoltaic devices. The purpose of this invention is to solve the technical problems of complex production processes, high energy consumption, high cost, low recovery rate, and limited applicability in existing waste lead-acid battery recycling processes. It provides a method for purifying halides from lead paste materials from waste lead-acid batteries, changing the traditional approach to lead paste recycling. This method is simple, easy to operate, consumes little energy, has a high recovery rate, produces high-purity recycled products, and does not generate wastewater or waste gas byproducts, achieving the goal of energy conservation and emission reduction.

Description

Technical Field

[0001] This invention belongs to the field of waste resource recycling and optoelectronic material preparation technology, specifically relating to a method for preparing perovskite light-emitting / photovoltaic devices by green recycling of lead metal from waste lead-acid batteries. Background Technology

[0002] Lead-acid batteries, due to their low price, mature technology, and reliable performance, have become the most produced and widely used secondary batteries among chemical power sources. They have long been widely used in various applications such as uninterruptible power supplies for automobiles and power sources for electric bicycles. However, while lead-acid batteries bring convenience to people's lives, they also pose hidden environmental pollution problems. Waste lead-acid batteries are rendered unusable due to problems such as water loss, sulfation, active material shedding, and plate softening. These discarded lead-acid batteries also put pressure on the environment; if not properly disposed of, the heavy metal lead in waste batteries can cause irreparable damage to water bodies, soil, and human health. Therefore, the reduced-volume and harmless recycling and disposal of waste lead-acid batteries aligns with the national sustainable development strategy.

[0003] Meanwhile, perovskite materials have shown outstanding performance in the fields of luminescence and photovoltaics, with advantages such as high photoelectric conversion efficiency, adjustable band gap, simple preparation process and low cost, making them a hot topic in current optoelectronic materials research. However, in the traditional perovskite material preparation process, high-purity chemical reagents are usually used as lead sources, which not only increases production costs, but also poses a challenge to the sustainable utilization of lead resources. Therefore, the application of lead metal and its compounds obtained from the recycling of waste lead-acid batteries to the new photovoltaic / optoelectronic industry is a new way to realize the resource utilization of metal waste. Using lead resources in lead-acid batteries to manufacture perovskite devices has two advantages: (1) It can reasonably and appropriately alleviate the environmental problems caused by waste lead-acid batteries, realize the recycling and utilization of lead resources for advanced applications; (2) It can increase the added value of lead resources and reduce the manufacturing cost of advanced optoelectronic devices.

[0004] In view of this, the present invention has derived a “wet-fire-wet” green recycling process through experiments, which involves wet desulfurization, pyrometallurgical calcination, and wet chemical halogenation. The recycled products PbI2 and PbBr2 are used to prepare perovskite precursor solutions, thereby preparing high-performance perovskite light-emitting / photovoltaic devices. Summary of the Invention

[0005] To address the pollution issues caused by solid waste and the cost problems of perovskite devices, this invention provides a method for recycling lead metal from spent lead-acid batteries to prepare perovskite light-emitting / photovoltaic devices. This invention recycles lead metal from spent lead-acid batteries using a green "wet-fire-wet" process involving wet desulfurization, pyrometallurgical calcination, and wet chemical halogenation, converting it into lead halide raw materials suitable for perovskite light-emitting / photovoltaic devices. This reduces environmental harm, saves on the cost of perovskite devices, and achieves the goal of turning waste into treasure.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries disclosed in this invention includes the following steps: Step 1: Pre-treatment of used lead-acid batteries The waste lead-acid batteries are disassembled, and components such as lead plates are separated. After removing surface impurities, the lead plates are ground into fine particles for subsequent processing.

[0008] Step 2: Desulfurization treatment Ammonium carbonate solution is added to the ground lead electrode particles, and a leaching reaction is carried out under certain temperature and stirring conditions, so that lead dissolves into the solution in ionic form, thereby achieving the purpose of desulfurization.

[0009] Step 3: Calcination treatment The lead carbonate, lead, and lead dioxide obtained from the desulfurization reaction are dried and calcined in a tube furnace at 500-700 ℃ for 4-6 hours to obtain yellow PbO powder.

[0010] Step 4: Preparation of lead halide The calcined PbO powder was reacted with 1-3 mol / L dilute nitric acid in a stoichiometric ratio to obtain a clear solution. Then, HI or HBr was added dropwise to the clear solution until no more yellow PbI2 or PbBr2 crystals were formed. The obtained PbI2 or PbBr2 crystals were washed with ethanol, purified with DMF, and recrystallized to obtain high-purity lead halide powder.

[0011] Step 5: Preparation of perovskite precursor solution Using recycled lead halides as the lead source, the components required for preparing the perovskite precursor solution include CsCl, CsBr, CsI, FACl, FABr, FAI, MACl, MABr, MAI, inorganic / organic additives, DMSO, and DMF. These are prepared according to a specific stoichiometric ratio and heated and stirred overnight for later use. For example, the molar ratio of lead salt, organic halide, and inorganic halide can be controlled within the range of 1:(1-1.2):(0-0.2) to obtain perovskite materials with good photoelectric properties.

[0012] Step Six: Preparation of Perovskite Thin Films Methods for preparing perovskite thin films include spin coating, coating, or vapor deposition, sometimes requiring chlorobenzene, toluene, ethyl acetate, or chloroform as antisolvents. During spin coating, the crystallinity, morphology, and thickness of the perovskite film can be controlled by adjusting parameters such as spin speed, time, and annealing temperature. For example, the spin coating speed can be set to 2000-5000 rpm, the spin coating time to 30-60 s, and the annealing temperature to 100-150 °C to obtain a dense, uniform, and well-crystallized perovskite film.

[0013] Step 7: Device Assembly and Packaging Electron transport layers and hole transport layers are deposited on the upper and lower layers of a perovskite thin film, and metal electrodes are fabricated, followed by encapsulation. The transport layer materials used for device assembly and encapsulation include C. 60 PEDOT: PSS, NiO x SnO x , ZnO, Spiro-OMeTAD, BCP, B3PY m Materials include PM and TPBi, and metal electrodes include Au, Ag, Cu, and Al. A glass cover and sealant are used for encapsulation to prevent moisture and oxygen in the air from affecting device performance, thereby improving device stability and lifespan.

[0014] It should be noted that in step one, the waste lead-acid batteries need to be physically dismantled, and the lead paste and lead mesh on the electrode plates need to be ground to ensure complete desulfurization in the subsequent reaction. In step two, due to the continuous charge-discharge cycle of lead-acid batteries, a large amount of PbSO4 is generated at both the anode and cathode, so desulfurization is performed first to facilitate the subsequent reaction. In step three, PbO powder is obtained by calcination. To address the new pollution caused by lead vapor, hydroiodic acid is used to treat the lead powder tail gas, and the product and excess hydroiodic acid can be reused. In step four, wet chemical halogenation uses dilute nitric acid and hydroiodic acid (hydrobromic acid) sequentially. To ensure the smooth progress of the reaction, direct reaction between PbO powder and hydroiodic acid (hydrobromic acid) should be avoided to prevent the formation of lead halide that covers the surface and hinders the reaction process. Furthermore, the subsequent purification process includes washing and recrystallization to ensure the purity of the lead halide.

[0015] According to a preferred embodiment of the present invention, the calcination temperature of lead carbonate, lead, and lead dioxide is 600 °C, and the calcination time is 5 h.

[0016] According to a preferred embodiment of the present invention, the concentration of dilute nitric acid reacting with PbO powder is 2 mol / L, and the concentration of HI is 57% by mass.

[0017] According to a preferred embodiment of the present invention, the molar ratio of FAI, PbI2, and 5AVA in the FAPbI3 solution used for preparing LED devices is 1.8:1.0:0.2, and the solution concentration is 0.5-1.0 M, preferably 0.7 M; the spin-coating process is 5000 rpm for 30 s, the acceleration is 5000 rpm / min, the antisolvent is chlorobenzene, the dropping volume is 100-200 μL, and the dropping time is 5-10 s after the start of spin-coating; the device structure is ITO / ZnO / perovskite / Spiro-OMeTAD / MoO x / Ag, and encapsulated with UV-curable adhesive.

[0018] According to a preferred embodiment of the present invention, the concentration of PbI2 solution used for fabricating PV devices is 1.0 M, the concentration of FAI+MABr+MACl solution is also 1.0 M, the spin-coating process is 5000 rpm for 60 s, and the acceleration is 2000 rpm / min; the device structure is ITO / SnO. X / Perovskite / Spiro-OMeTAD / MoO x / Ag, and encapsulated with UV-curable adhesive.

[0019] According to a preferred embodiment of the present invention, except for the electron transport layer, the perovskite active layer and the hole transport layer are prepared in a protective gas atmosphere, wherein the protective gas is nitrogen.

[0020] This invention further discloses a method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries. The purity of the recovered lead iodide is as high as 99% or more, with a recovery rate of 93.1%. The EQE of LEDs prepared using the recovered lead iodide is 18.7% (the EQE of devices prepared using commercial lead iodide is 19.0%), and the PCE of solar cells is 23.56% (the PCE of devices prepared using commercial lead iodide is 23.91%).

[0021] Compared with the prior art, the beneficial effects of the present invention are: (1) This invention proposes a more universal “wet-fire-wet” process, firstly using wet dissolution and leaching to separate the products, then using fire calcination to calcine lead oxide, and finally using wet process to obtain lead halides (PbI2, PbBr2). The entire recycling process greatly reduces the generation of waste gas, wastewater and waste residue, which is in line with the concept of environmental protection and provides a new idea for solving the environmental problems of hazardous solid waste. (2) The purity of the recovered product of this invention is greater than 99%, the recovery rate is greater than 90%, and the recovery cost is lower than the market price; (3) The present invention utilizes the recycled lead halide to prepare perovskite light-emitting / photovoltaic devices. Taking lead iodide as an example, the prepared LED has an EQE of 18.7% (commercial EQE is 19.0%) and a PCE of 23.56% (commercial PCE is 23.91%), which is comparable to the performance of devices prepared with commercial lead iodide, indicating that the recycled products of the present invention can be industrially produced. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0023] Figure 1 This is a flow chart of the "wet-fire-wet" process implemented in this invention.

[0024] Figure 2 The image shows the lead oxide powder after calcination (left) and the EDS test result of lead oxide (right) in this invention. The purity of lead oxide exceeds 99.5%.

[0025] Figure 3 The image shows the lead iodide powder recovered by this invention (left) and the XRD test image of the lead iodide powder (right), which are consistent with the XRD standard card of commercial lead iodide.

[0026] Figure 4 The image shows the lead bromide powder recovered by this invention (left) and the XRD test image of the lead bromide powder (right), which are consistent with the XRD standard card of commercial lead bromide.

[0027] Figure 5 This invention provides the fabrication process for the perovskite light-emitting device and perovskite solar cell.

[0028] Figure 6 The EQE test results (A) and current-voltage-luminance curve (B) of the perovskite light-emitting device prepared from lead iodide recovered in this invention are shown.

[0029] Figure 7 The brightness diagram (left) and brightness test result curve (right) of the perovskite light-emitting device prepared from lead bromide recovered in this invention.

[0030] Figure 8 The PCE test results are for the perovskite solar cells prepared from lead iodide recovered in this invention. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0033] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0034] In the description of this invention, it should be understood that the terms "middle", "upper", "lower", "rise", "fall", "vertical", "surface", "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 invention 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 invention.

[0035] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0036] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0037] This invention discloses a method for preparing high-performance perovskite light-emitting / photovoltaic devices by green recycling of lead metal from waste lead-acid batteries.

[0038] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0039] Example 1: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries, wherein the process of preparing FAPbI3 light-emitting diodes using recycled lead iodide is as follows: Step 1: Pre-treatment of used lead-acid batteries The waste lead-acid batteries are disassembled, and components such as lead plates are separated. After removing surface impurities, the lead plates are ground into fine particles for subsequent processing.

[0040] Step 2: Desulfurization treatment Add ammonium carbonate solution (2 mol / L) to the ground lead electrode particles. -1 The solution is stirred at room temperature (25 ℃) to carry out a leaching reaction, so that lead enters the lead carbonate precipitate in the form of ions. The lead carbonate is then washed and dried to achieve the purpose of desulfurization.

[0041] Step 3: Calcination treatment The lead carbonate, lead, and lead dioxide obtained from the desulfurization reaction were dried and calcined in a tube furnace at 600 °C for 5 h to obtain yellow PbO powder.

[0042] Step 4: Preparation of lead halide The calcined PbO powder was reacted with 2 mol / L dilute nitric acid at a molar ratio of 2:1 to obtain a clear solution. Then, 57% HI was added dropwise to the clear solution until no more yellow PbI2 crystals were formed. The obtained PbI2 crystals were washed with ethanol, purified with DMF, recrystallized, washed, and dried to obtain high-purity lead iodide powder.

[0043] Step 5: Preparation of perovskite precursor solution Using recovered lead iodide as the lead source, it was mixed with the components FAI and 5AVA required for the preparation of the perovskite precursor solution in a stoichiometric ratio of 1.0:1.8:0.2 and heated and stirred overnight for later use.

[0044] Step Six: Preparation of Perovskite Thin Films Perovskite films were prepared by spin coating. The spin coating speed was set to 5000 rpm, the spin coating time was 30 s, and the annealing temperature was 150 ℃. Chlorobenzene (99.9%) was used as the anti-solvent, and 200 μL was added dropwise 7 s after the start of spin coating to obtain dense, uniform and well-crystallized perovskite films.

[0045] Step 7: Device Assembly and Packaging 30 nm ZnO, perovskite, 30 nm Spiro-OMeTAD, and 5 nm MoO were sequentially deposited on a clean ITO conductive glass. xThe device is encapsulated with 100 nm Ag and then sealed with a glass cover and sealant to prevent moisture and oxygen in the air from affecting the device performance, thereby improving the device's stability and lifespan.

[0046] Within the integrating sphere, the light-emitting diode fabricated in this embodiment based on a perovskite thin film using recycled lead iodide as the lead source has an EQE of 18.7% and a radiance of 173 W sr. -1 m -2 .

[0047] Example 2: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries, wherein the process of preparing CsPbBr3 light-emitting diodes using recycled lead bromide is as follows: The process for preparing CsPbBr3 light-emitting diodes using recycled lead bromide is as described in Example 1, except that: In step four, the lead solution after reacting with nitric acid is reacted with HBr, and the resulting PbBr2 crystals are washed with ethanol, purified with DMF, recrystallized, washed, and dried to obtain high-purity lead bromide powder.

[0048] In step five, the recovered lead bromide is used as the lead source and mixed with the components CsBr and MABr required for the preparation of the perovskite precursor solution in a stoichiometric ratio of 1.0:1.0:0.1. The mixture is heated and stirred overnight for later use.

[0049] In step six, a perovskite film is prepared by spin coating. The spin coating speed can be set to 3000 rpm, the spin coating time is 60 s, the annealing temperature is 80 ℃, and chlorobenzene (99.9%) is used as the anti-solvent. 200 μL is added dropwise 30 s after the start of spin coating to obtain a dense, uniform and well-crystallized perovskite film.

[0050] In step seven, 30 nm PEDOT: PSS, perovskite, 30 nm TPBi, 1 nm LiF, and 100 nm Al are sequentially deposited on a clean ITO conductive glass. Then, a glass cover plate and sealant are used for encapsulation to prevent moisture and oxygen in the air from affecting the device performance and to improve the stability and lifespan of the device.

[0051] The other steps and conditions are the same as in Example 1.

[0052] like Figure 7 As shown, within the integrating sphere, the luminance of the light-emitting diode fabricated in this embodiment based on a perovskite thin film using recycled lead bromide as the lead source is 2174 cd / m². -2 .

[0053] Example 3: A method for preparing high-performance perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries, wherein the process of preparing FAPbI3 solar cells using recycled lead iodide is as follows: The process for preparing FAPbI3 solar cells using recycled lead bromide is the same as described in Example 1, except that: In step five, the recovered lead iodide is used as the lead source and is mixed with the components FAI, MAI and MACl required for the preparation of the perovskite precursor solution in a stoichiometric ratio of 1.0:0.9:0.1:0.05. The mixture is heated and stirred overnight for later use.

[0054] Step Six: Preparation of Perovskite Thin Films Perovskite thin films were prepared by spin coating. The spin coating speed was set to 2000 rpm, the spin coating time was 60 s, and the annealing temperature was 150 ℃. At the 8th second of the spin coating process, 200 μL of chlorobenzene was added as an anti-solvent to obtain a dense, uniform and well-crystallized perovskite thin film.

[0055] Step 7: Device Assembly and Packaging 30 nm SnOx, perovskite, 30 nm Spiro-OMeTAD, and 5 nm MoO were sequentially deposited on a clean ITO conductive glass. x The device is encapsulated with 100 nm Au, and then sealed with a glass cover and sealant to prevent moisture and oxygen in the air from affecting the device performance, thereby improving the device's stability and lifespan.

[0056] The other steps and conditions are the same as in Example 1.

[0057] like Figure 8 As shown, under standard test conditions (AM 1.5 G), the PCE of the reverse scan of the solar cell device based on FAPbI3 perovskite thin film in this embodiment is 23.91%. V oc It is 1.16 V. J sc 25.27 mA cm -2 FF is 81.75%.

[0058] Example 4: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries, wherein the process of preparing FAPbI3 light-emitting diodes using recycled lead iodide is as follows: Step 1: Pre-treatment of used lead-acid batteries The waste lead-acid batteries are disassembled, and components such as lead plates are separated. After removing surface impurities, the lead plates are ground into fine particles for subsequent processing.

[0059] Step 2: Desulfurization treatment Add ammonium carbonate solution (2 mol / L) to the ground lead electrode particles. -1 The solution is stirred at room temperature (25 ℃) to carry out a leaching reaction, so that lead enters the lead carbonate precipitate in the form of ions. The lead carbonate is then washed and dried to achieve the purpose of desulfurization.

[0060] Step 3: Calcination treatment The lead carbonate, lead, and lead dioxide obtained from the desulfurization reaction were dried and then calcined in a tube furnace at 300 ℃, 400 ℃, and 500 ℃ for 3 h, 4 h, and 5 h, respectively, to obtain yellow PbO powder.

[0061] Step 4: Preparation of lead halide The calcined PbO powder was reacted with 2 mol / L dilute nitric acid at a molar ratio of 2:1 to obtain a clear solution. Then, 57% HI was added dropwise to the clear solution until no more yellow PbI2 crystals were formed. The obtained PbI2 crystals were washed with ethanol, purified with DMF, recrystallized, washed, and dried to obtain high-purity lead iodide powder.

[0062] Step 5: Preparation of perovskite precursor solution Using recovered lead iodide as the lead source, it was mixed with the components FAI and 5AVA required for the preparation of the perovskite precursor solution in a stoichiometric ratio of 1.0:1.8:0.2 and heated and stirred overnight for later use.

[0063] Step Six: Preparation of Perovskite Thin Films Perovskite films were prepared by spin coating. The spin coating speed was set to 5000 rpm, the spin coating time was 30 s, and the annealing temperature was 150 ℃. Chlorobenzene (99.9%) was used as the anti-solvent, and 200 μL was added dropwise 7 s after the start of spin coating to obtain dense, uniform and well-crystallized perovskite films.

[0064] Step 7: Device Assembly and Packaging 30 nm ZnO, perovskite, 30 nm Spiro-OMeTAD, and 5 nm MoO were sequentially deposited on a clean ITO conductive glass. x The device is encapsulated with 100 nm Ag and then sealed with a glass cover and sealant to prevent moisture and oxygen in the air from affecting the device performance, thereby improving the device's stability and lifespan.

[0065] Within the integrating sphere, the light-emitting diode fabricated in this embodiment based on a perovskite thin film using recycled lead iodide as the lead source has an EQE of 12.2% and a radiance of 92 W sr. -1 m -2 .

[0066] To further demonstrate the beneficial effects of the present invention and to better understand it, the following experimental examples and comparative examples further illustrate the technical features disclosed in the present invention, but should not be construed as limiting the present invention. Other improvements made by those skilled in the art based on the above-described invention, without inventive effort, are also considered to fall within the protection scope of the present invention.

[0067] Comparative Example 1: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries is disclosed, as described in Example 1, except that the lead source used in the FAPbI3 perovskite precursor solution in step five is commercial lead iodide. Other steps and conditions are consistent with Example 1.

[0068] Within the integrating sphere, the light-emitting diode fabricated in this embodiment based on a perovskite thin film using recycled lead iodide as the lead source has an EQE of 19.0% and a radiance of 178 W sr. -1 m -2 .

[0069] The perovskite light-emitting devices prepared in step seven of Example 1 and Comparative Example 1 exhibit the following performance: Figure 6 As shown in the figure, the performance of the recovered lead iodide is comparable to that of devices made from commercial lead iodide, indicating that the purity of the recovered lead iodide is sufficient to serve as a lead source for perovskite light-emitting diodes.

[0070] Comparative Example 2: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries is described in Example 2, except that the lead source used in the CsPbBr3 perovskite precursor solution in step five is commercial lead bromide. Other steps and conditions are the same as in Example 2.

[0071] Within the integrating sphere, the light-emitting diode fabricated in this embodiment based on a perovskite thin film using recycled lead bromide as the lead source has a brightness of 2174 cd / m². -2 .

[0072] The performance of the perovskite light-emitting devices prepared in step seven of Example 2 and Comparative Example 2 is as follows: Figure 7 As shown in the figure, the recovered lead bromide has performance comparable to devices made from commercial lead bromide, indicating that the purity of the recovered lead bromide is sufficient to serve as a lead source for perovskite light-emitting diodes.

[0073] Comparative Example 3: A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries is described in Example 3, except that the lead source used in the FAPbI3 perovskite precursor solution in step five is commercial lead iodide. Other steps and conditions are the same as in Example 3.

[0074] like Figure 8 As shown, under standard test conditions (AM 1.5 G), the PCE of the reverse scan of the solar cell device based on FAPbI3 perovskite thin film in this embodiment is 23.56%. V oc It is 1.15 V. J sc 25.43 mA cm -2 FF was 80.47%.

[0075] The perovskite solar cells prepared in step seven of Example 3 and Comparative Example 3 exhibit the following performance: Figure 8 As shown in the figure, the performance of the recovered lead iodide is comparable to that of devices made from commercial lead iodide, indicating that the purity of the recovered lead iodide is sufficient to serve as a lead source for perovskite solar cells.

[0076] Table 1. Cost and recovery rate of the lead-acid battery recycling process of this invention.

[0077] As shown in Table 1, while ensuring device efficiency, the cost of lead iodide obtained by recycling waste lead-acid batteries is significantly lower than the price of commercial lead iodide, greatly reducing device manufacturing costs. The cost of lead iodide obtained by recycling waste lead-acid batteries is only 13.6% of the price of laboratory-grade commercial lead iodide (3.99 USD / g) and 70.2% of the price of industrial-grade commercial lead iodide (0.0092 USD / g). Furthermore, the recovery rate of recycled lead-acid batteries reaches 93.1%, which is far higher than the current commercial rate of 90% while obtaining high-purity (99.9%) lead iodide products.

[0078] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries, characterized in that, Waste lead-acid batteries are recycled using a "wet-fire-wet" green process. The disassembled electrode plates undergo desulfurization, calcination, and halogenation processes, and are then recrystallized to obtain lead halides (PbI2 and PbBr2). These halides are then used as raw materials to prepare high-performance perovskite light-emitting / photovoltaic devices. The method includes the following steps: Step 1: Disassembly process. Remove the cathode and anode of the used lead-acid battery and crush them for later use. Step 2: Desulfurization treatment. Add ammonium carbonate solution to lead paste to cause lead ions and carbonate ions to form insoluble lead carbonate precipitate. Then filter, wash and dry the precipitate to achieve the purpose of desulfurization. Step 3: Calcination treatment. The lead carbonate, lead and lead dioxide obtained from the desulfurization reaction are calcined in a tube furnace at 500-700 ℃ for 4-6 h to obtain yellow PbO powder. Step 4: Preparation of lead halide. The calcined PbO powder is reacted with 1-3 mol / L dilute nitric acid in stoichiometric ratio to obtain a clear solution. Then, HI or HBr is added dropwise to the transparent solution until no more yellow PbI2 or PbBr2 crystals are formed. The obtained PbI2 or PbBr2 crystals are washed with ethanol, purified with DMF, recrystallized, centrifuged, and dried to obtain lead halide powder. Step 5: Preparation of perovskite precursor solution. Using recovered lead halide as the lead source, the perovskite precursor solution is prepared by mixing it with organic halides, inorganic halides and organic solvents. Step 6: Preparation of perovskite thin film. The prepared perovskite precursor solution is deposited on a conductive substrate using spin coating, blade coating or vapor deposition to form a perovskite thin film. Step 7: Device assembly and packaging. Electron transport layers and hole transport layers are deposited on the upper and lower layers of the perovskite thin film, and metal electrodes are prepared. Then, the film is packaged to finally obtain the perovskite light-emitting / photovoltaic device.

2. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step one, the waste lead-acid batteries need to be physically dismantled. The lead paste and lead mesh on the electrode plates are ground in a crusher and a mortar to ensure that the subsequent desulfurization reaction is complete.

3. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step two, due to the continuous charge-discharge cycle of the lead-acid battery, a large amount of PbSO4 (70 wt%) will be generated at both the anode and cathode. Therefore, desulfurization treatment is carried out first, that is, PbSO4 and ammonium carbonate solution are reacted at room temperature with stirring in a 1:1 molar ratio to generate lead carbonate precipitate and ammonium sulfate. The precipitate is washed and dried with deionized water to obtain lead carbonate for subsequent reactions.

4. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step four, wet chemical halogenation involves reacting lead oxide (both in a molar ratio of 2:1) with dilute nitric acid and hydroiodic acid (hydrobromic acid) at room temperature with stirring. To ensure the smooth progress of the reaction, direct reaction between PbO powder and hydroiodic acid (hydrobromic acid) should be avoided to prevent the formation of lead halide that would cover the surface and hinder the reaction process. Furthermore, subsequent purification processes, including washing and recrystallization, ensure the purity of the lead halide.

5. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step five, the components required for the preparation of the perovskite precursor solution are CsCl, CsBr, CsI, FACl, FABr, FAI, MACl, MABr, MAI, 5-aminovaleric acid molecules, DMSO, and DMF. They are prepared according to a certain stoichiometric ratio and heated and stirred overnight for later use.

6. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step six, the methods used to prepare the perovskite thin film include spin coating, coating or vapor deposition. Sometimes an anti-solvent is required, which includes one or more combinations of chlorobenzene, toluene, ethyl acetate and chloroform.

7. The method for preparing perovskite light-emitting / photovoltaic devices by recycling lead metal from waste lead-acid batteries according to claim 1, characterized in that, In step seven, the transport layer material used for device assembly and packaging includes C. 60 PEDOT: PSS, NiO x SnO x , ZnO, Spiro-OMeTAD, BCP, B3PY m PM and TPBi, with metal electrodes including Au, Ag, Cu, and Al, are encapsulated using UV-curable adhesive.

8. A perovskite light-emitting / photovoltaic device made by the recycling method of any one of claims 1-7, wherein lead halide obtained from the recycling of waste lead-acid batteries is used as the raw material of the device.

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