Process and application for recycling lead and transparent conductor substrate

Abstract

The invention provides a lead and transparent conductor substrate recycling process and application, and belongs to the technical field of photovoltaics. Comprising the following steps that the perovskite cell is soaked in a first organic solvent, a metal electrode material falls off after a transmission layer material is dissolved, a transmission layer solution and the metal electrode material are obtained through filtering, and the rest part of the perovskite cell is decomposed perovskite cell; transferring the decomposed perovskite cell into a second organic solvent for cleaning to obtain a conductor substrate glass and a lead-containing mixed solution; removing moisture and an organic solvent from the lead-containing mixed solution, and calcining to obtain lead oxide; the conductor substrate glass, the transmission layer organic material and lead oxide are assembled into a battery for reuse; the first organic solvent is at least one of benzenes, alcohols, ketones, chloroform, esters and ethers; the second organic solvent is a chelating agent solution. The process provided by the invention is low in cost and simple to operate, and the photoelectric conversion efficiency of the recovered and assembled battery can still be comparable with that of a primary battery.

Description

Technical Field

[0001] The present invention provides a process and application for the recycling of lead and a transparent conductor substrate, belonging to the field of photovoltaic technology. Background Art

[0002] Perovskite solar cells offer the advantages of high efficiency and low cost in solar cell technology. However, as technology advances, increasing solar cell waste is becoming a potential threat. To achieve environmentally friendly and cost-effective commercialization of perovskite solar cells, managing the entire perovskite process lifecycle is crucial. Efforts are underway to develop recycling technologies to support the sustainable development of perovskites.

[0003] Once perovskite solar cells are put into operation, it only takes less than a year to offset the energy consumption of manufacturing the device. In the entire energy consumption process, the glass substrate with conductive oxides and energy-intensive heating process is the main factor causing environmental changes. Recycling its conductive oxide glass substrate can play an important role in reducing energy consumption, energy production, and environmental protection. At the same time, eliminating the impact of toxic elements Pb and harmful solvents is also a challenging direction for the sustainable development of perovskite solar cells (PSCs). Therefore, in the recycling cycle, achieving the full life cycle management of toxic lead is also a key step in the effective management of the entire life cycle of perovskites.

[0004] Chinese patent CN107513618B discloses a method and apparatus for recovering lead from perovskite batteries, comprising the following steps: crushing the perovskite battery into fragments; soaking the fragments in a soaking solution, followed by solid-liquid separation to obtain a lead-containing separated liquid; the soaking solution comprises an organic solvent capable of dissolving the perovskite material; and subjecting the lead-containing separated liquid to a chemical precipitation or electrolysis operation to obtain a lead-containing solid. This lead recovery method for perovskite batteries recovers lead, thereby avoiding lead pollution and being environmentally friendly. However, this patent does not recycle the electrolytic glass substrate, resulting in a waste of resources. Furthermore, the lead recovery method employed is electrolysis, which consumes a lot of energy.

[0005] Deng Fei disclosed methods for recycling key components (PbI2, ITO, and Ag) and lead in his research on the recycling and utilization of key materials and device integration processes for sustainable perovskite solar cells (doctoral dissertation at Beijing University of Chemical Technology). Recycling of the ITO transparent conductive electrode: Use a single-sided blade to scrape off the top carbon electrode to expose the severely decomposed perovskite photoactive layer. Then, use a DMF / DMSO mixed solution to dissolve the decomposed perovskite photoactive layer. Once fully dissolved, remove the ITO electrode and move it to a cleaning rack for a deep clean to remove residual SnO2 and carbon residue on the surface. Then, blow dry with nitrogen and seal. Recycling of PbI2: For MAPbI3 devices, place the DMF / DMSO mixed solution containing the severely decomposed perovskite on a constant temperature heating table at 100°C for drying. The volatilized DMF and DMSO are absorbed by the activated carbon unit and will not pollute the external environment. The remaining yellow powder is PbI2. However, DMF and DMSO are miscible with water and have high boiling points and are not easily volatile. They are also highly toxic substances and are difficult to handle. At the same time, the process of this article requires scraping off the top layer of carbon electrode with a single-sided blade, which is a cumbersome and complicated operation. Summary of the Invention

[0006] In order to address the deficiencies in the prior art, the present invention provides a process and application for the recycling and utilization of lead and transparent conductor substrates. The process of the present invention has low cost and simple operation, and the photoelectric conversion efficiency of the recycled and assembled batteries is still comparable to that of the original batteries.

[0007] To achieve the above objectives, the technical solutions provided by the present invention are as follows:

[0008] In a first aspect, the present invention provides a process for recycling lead and a transparent conductor substrate, comprising the following steps:

[0009] (1) immersing the perovskite battery in a first organic solvent, dissolving the transport layer material and causing the metal electrode material to fall off, filtering to obtain the transport layer solution and the metal electrode material, and the remaining portion of the perovskite battery being the decomposed perovskite battery;

[0010] (2) transferring the decomposed perovskite cell obtained in step (1) to a second organic solvent for cleaning to obtain a mixed solution of the conductive substrate glass and the lead-containing solution;

[0011] (3) removing water and organic solvent from the lead-containing mixed solution obtained in step (2), and then calcining to obtain lead oxide;

[0012] (4) Assembling a battery with the conductive substrate glass obtained in step (2), the transmission layer solution obtained in step (1) and the lead oxide obtained in step (3) for reuse; the lead oxide needs to be prepared into a lead-containing salt.

[0013] The first organic solvent is at least one of benzene, alcohols, ketones, chloroform, esters and ethers;

[0014] The second organic solvent is a chelating agent solution.

[0015] Furthermore, the conductive substrate glass contains an oxide conductor.

[0016] Preferably, the oxide conductor includes SnO2, NiO x , ZnO and TiO2.

[0017] Furthermore, the calcination temperature in step (3) is 400-600° C. and the calcination time is 20-40 min.

[0018] Furthermore, the first organic solvent is a mixed solution of benzene and at least one of ethers, alcohols, and ketones.

[0019] Preferably, the first organic solvent is a mixed solvent of benzene and alcohol reagents.

[0020] Furthermore, the volume ratio of the benzene and alcohol reagents is 100:1 to 1:100.

[0021] Preferably, the volume ratio of the benzene and alcohol reagents is (1-5):1.

[0022] Furthermore, the benzene is at least one of toluene, chlorobenzene and xylene.

[0023] Preferably, the benzene is chlorobenzene.

[0024] Further, the ketone is acetylacetone;

[0025] Furthermore, the alcohol reagent is at least one of ethanol, n-butanol, and isopropanol.

[0026] Preferably, the alcohol reagent is n-butanol.

[0027] Furthermore, the ester is ethyl acetate; and the ether is diethyl ether.

[0028] Further preferably, the volume ratio of chlorobenzene to n-butanol is (1-3):1.

[0029] More preferably, the volume ratio of chlorobenzene to n-butanol is (1-2):1.

[0030] Furthermore, the chelating agent is a carboxylic acid compound, polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, or polyamine.

[0031] Preferably, the chelating agent is a carboxylic acid compound.

[0032] Furthermore, the carboxylic acid compound is at least one of formic acid, acetic acid, citric acid, malic acid, tartaric acid and lactic acid.

[0033] Preferably, the carboxylic acid compound is at least one of citric acid and malic acid.

[0034] Furthermore, the solvent of the carboxylic acid compound solution is at least one of chlorobenzene, water, ethanol and diethyl ether.

[0035] Furthermore, the concentration of the chelating agent solution is 0-10 mol / L.

[0036] Preferably, the concentration of the chelating agent solution is 0.1-1 mol / L.

[0037] Further preferably, the concentration of the chelating agent solution is 0.1-0.5 mol / L.

[0038] More preferably, the concentration of the chelating agent solution is 0.1-0.25 mol / L.

[0039] In a second aspect, the present invention provides a battery obtained by the above process.

[0040] In a third aspect, the present invention provides application of the above process in battery preparation.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The process of the present invention realizes the recycling of the conductive glass substrate, which accounts for more than 50% of the component cost, reduces the component battery cost, reduces the one-time consumption of raw materials in component production, and reduces carbon emissions.

[0043] (2) The recycling process has fewer steps and is simple. The solvents used are cheap and readily available, making them easy to industrialize and reuse. The solvents used in the process can be recycled multiple times.

[0044] (3) Using carboxylic acid materials to assist in the recovery of conductive glass substrates not only allows for efficient and cleaner recovery of conductive glass substrates, but also preserves the performance of the original conductive glass substrates, allowing them to be used in tissue batteries. Simultaneously, this allows for the controlled recycling of lead source materials, thereby achieving environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 It is an implementation flow chart.

[0046] Figure 2 This is the appearance of the perovskite cell after cleaning with the first solvent in Example 1.

[0047] Figure 3This is the appearance of the perovskite cell in Example 1 after cleaning with the second solvent.

[0048] Figure 4 This is an SEM image of the glass substrate surface after cleaning with the second solvent in Example 1.

[0049] Figure 5 This is the SEM image of the glass substrate surface originally loaded with SnO2 thin film.

[0050] Figure 6 This is the surface SEM image of conductive glass ITO.

[0051] Figure 7 These are the appearance pictures of Comparative Examples 2 and 3. DETAILED DESCRIPTION

[0052] In order to make the technical means, creative features, purpose and effect of the present invention easy to understand, the present invention is further illustrated below in conjunction with specific embodiment, but the following embodiment is only a preferred embodiment of the present invention, not all. Based on the embodiment in the embodiment, other embodiments obtained by those skilled in the art without making creative work all fall within the protection scope of the present invention. It is worth noting that the raw materials used in the present invention are all common commercial products, and their source is not specifically limited. The technology and scientific terms used in the embodiment have the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0053] Unless otherwise specified, the concentrations described in the present invention are all mass concentrations.

[0054] The present invention does not limit the sources of the raw materials used. Unless otherwise specified, the raw materials used in the present invention are common commercial products in the technical field.

[0055] The "ranges" disclosed herein are in the form of lower limits and upper limits. There can be one or more lower limits, and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit.

[0056] The lower and upper limits define the boundaries of a particular range. All ranges that can be limited in this way are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60-120 and 80-110 is listed for a particular parameter, it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and if the maximum range values ​​listed are 3, 4, and 5, then the following ranges can all be expected: 1-2, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0057] In this disclosure, unless otherwise specified, the numerical range "ab" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is merely an abbreviation for these numerical combinations.

[0058] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0059] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0060] The following is an example:

[0061] SnO2 solution (15 wt% aqueous solution), lead iodide (PbI2, 99.9%), and N,N-dimethylformamide (DMF, 99.9%) were purchased from Alfa-Aesar; lead bromide (PbBr2, 99.9%), dimethyl sulfoxide (DMSO, 99.5%), cesium iodide (CsI, 99%), and chlorobenzene (CB, 99.5%) were purchased from Sigma-Aldrich. Methylamine bromide (MABr, 99.9%), formamidinium iodide (FAI, 99.9%), Spiro-OMeTAD, and 4-tert-butylpyridine (t-BP) were purchased from Xi'an Biolight; citric acid (90%) was purchased from Titan Reagent Platform. All materials used were not further processed.

[0062] 1. Examples and Comparative Examples

[0063] Preparation of the pristine perovskite cell: 10 mL of a 5 wt% SnO₂ aqueous solution was spin-coated onto conductive ITO glass and calcined at 150°C for 30 minutes to form a SnO₂ thin film. A 1.4 mol / mL perovskite solution (545.4 mg of PbI₂, 79.6 mg of PbBr₂, 195.0 mg of FAI, 18.1 mg of CsI, and 21.9 mg of MABr dissolved in 1 mL of DMF / DMSO (7:3 by volume) was prepared and heated at 60°C with stirring for 1 hour.

[0064] Then, 30-50 μL of the perovskite solution was spin-coated on the SnO2 film substrate, and the corresponding perovskite absorber layer was formed using a toluene anti-solvent process. After the perovskite film prepared above was cooled, the modified Spiro-OMeTAD chlorobenzene solution was spin-coated, and after natural drying, a silver electrode (80 nm thick) was evaporated to assemble the corresponding perovskite solar cell. Through a solar simulator, at 100 mW cm -2The photoelectric conversion efficiency was tested under standard light. The effective area of ​​the cell is 0.0625 cm 2 .

[0065] Example 1

[0066] Cleaning in the first solvent: The degraded perovskite battery prepared above was immersed in a mixed solution of chlorobenzene and n-butanol (volume ratio 2:1) and ultrasonicated for 5 minutes. After the transport layer material was dissolved, the metal electrode material fell off. The transport layer solution and the metal electrode material were filtered to obtain the transport layer solution and the metal electrode material respectively. The remaining part of the perovskite battery was the decomposed perovskite battery. Figure 2 This is a photo of the appearance of the decomposed perovskite cell after the first solvent cleaning.

[0067] Preparation of the second citric acid solvent: Dissolve 10 mmol of citric acid in 20 ml of aqueous solution under stirring at room temperature, and then add 20 ml of chlorobenzene solution to complete the preparation of the second solvent.

[0068] Recovery of the conductive substrate of SnO2 oxide: The decomposed perovskite cell is then taken out and placed in a second citric acid solvent for ultrasonic cleaning for 5 minutes. The glass sheet is taken out and ultrasonically cleaned with water and ethanol for 3 minutes in turn to obtain a conductive substrate containing SnO2 oxide. Figure 3 This is a photo of the appearance of the perovskite cell after cleaning with the second solvent. Figure 4 This is an SEM image of the glass substrate surface after cleaning with the second solvent.

[0069] Recovery of PbO: After the perovskite is immersed in the above-mentioned citric acid second solvent and used for multiple degradation, the lower chlorobenzene solution is separated and extracted by utilizing the insolubility of chlorobenzene in aqueous solution. The upper solution containing lead is placed in an oven, baked at 100°C for 5 hours, and then calcined at 500°C for 30 minutes.

[0070] Reuse of SnO2 oxide conductive substrate: The recovered SnO2 oxide conductive substrate is cleaned in an ozone cleaner for 20 minutes, and then directly spin-coated with a perovskite solution and a subsequent hole layer, and the upper electrode is evaporated to assemble into a complete battery.

[0071] Example 2

[0072] Cleaning in the first solvent: Same as in Example 1.

[0073] Preparation of the second malic acid solvent: Dissolve 10 mmol of malic acid in 20 ml of aqueous solution under stirring at room temperature, and then add 20 ml of chlorobenzene solution to complete the preparation of the second solvent.

[0074] Recovery of the conductive substrate of SnO2 oxide: The battery was then taken out and placed in a second malic acid solvent for ultrasonic cleaning for 5 minutes. The glass sheet was taken out and ultrasonically cleaned with water and ethanol for 3 minutes in sequence to obtain a conductive substrate containing SnO2 oxide.

[0075] Recovery of PbO: Same as Example 1.

[0076] Recycling of the conductive substrate of SnO2 oxide: Same as Example 1.

[0077] Comparative Example 1

[0078] No recycled materials were used. The original SnO2 film was prepared by preparing 10 mL of 5 wt% SnO2 aqueous solution, which was then spin-coated on the conductive glass ITO and calcined at 150°C for 30 min to form a SnO2 film.

[0079] Assembly of perovskite cells: same as preparation of original perovskite cells.

[0080] Figure 5 It corresponds to the prepared SnO2 film.

[0081] Figure 6 This is the surface SEM image of conductive glass ITO.

[0082] Comparative Example 2

[0083] Cleaning in the first solvent: Same as in Example 1.

[0084] Preparation of the second fumaric acid solvent: 10 mmol of fumaric acid was dissolved in 20 ml of aqueous solution under stirring at room temperature, and then 20 ml of chlorobenzene solution was added to complete the preparation of the second solvent.

[0085] Recovery of the conductive substrate of SnO2 oxide: The battery was then taken out and placed in a second solvent of fumaric acid and malic acid for ultrasonication for 5 minutes. The glass sheet was taken out and ultrasonically cleaned with water and ethanol for 3 minutes in sequence to obtain a conductive substrate containing SnO2 oxide.

[0086] Recovery of PbO: Same as Example 1.

[0087] Comparative Example 3

[0088] The first solvent was replaced with water and ethanol. The cleaning steps in the first solvent were the same as those in Example 1.

[0089] Preparation of the second malic acid solvent: Dissolve 10 mmol of malic acid in 20 ml of aqueous solution under stirring at room temperature, and then add 20 ml of chlorobenzene solution to complete the preparation of the second solvent.

[0090] Recovery of the conductive substrate of SnO2 oxide: The battery was then taken out and placed in a second malic acid solvent for ultrasonic cleaning for 5 minutes. The glass sheet was taken out and ultrasonically cleaned with water and ethanol for 3 minutes in sequence to obtain a conductive substrate containing SnO2 oxide.

[0091] Recovery of PbO: Same as Example 1.

[0092] from Figure 7 It can be seen from the battery appearance pictures that the bases of Comparative Examples 2 and 3 cannot be cleaned properly and the batteries cannot be assembled normally.

[0093] 2. Test Case

[0094] 1. Photoelectric conversion efficiency test

[0095] Through the solar simulator, at 100mW cm -2 Under standard light irradiation, the photoelectric conversion efficiency of the cells of Examples 1 and 2, and Comparative Example 1 was tested. The results are shown in Table 1.

[0096] Table 1

[0097]

[0098] Compared with Comparative Example 1 (a battery prepared without recycled materials), the photoelectric conversion efficiency of the recycled SnO2-based batteries (Examples 1-2) maintained 97.6% and 101.3% of the original battery photoelectric conversion efficiency, which is comparable to the original SnO2-based batteries.

[0099] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A process for recycling lead and transparent conductor substrates, characterized in that: The following steps are involved: (1) immersing the perovskite battery in a first organic solvent, dissolving the transport layer material and causing the metal electrode material to fall off, filtering to obtain the transport layer solution and the metal electrode material, and the remaining portion of the perovskite battery being the decomposed perovskite battery; (2) transferring the decomposed perovskite cell obtained in step (1) to a second organic solvent for cleaning to obtain a mixed solution of the conductive substrate glass and the lead-containing solution; (3) removing water and organic solvent from the lead-containing mixed solution obtained in step (2), and then calcining to obtain lead oxide; (4) assembling a battery with the conductive substrate glass obtained in step (2), the transport layer organic material solution obtained in step (1), and the lead oxide obtained in step (3) for reuse; The first organic solvent is at least one of benzene, alcohols, ketones, chloroform, esters and ethers; The second organic solvent is a chelating agent solution.

2. The process for recycling lead and transparent conductor substrate according to claim 1, characterized in that: The calcination temperature in step (3) is 400-600° C. and the calcination time is 20-40 min.

3. The process for recycling lead and transparent conductor substrate according to claim 1, characterized in that: The first organic solvent is a mixed solution of benzene and at least one of ether, alcohol, and ketone reagents, preferably a mixed solution of benzene and alcohol reagents.

4. The process for recycling lead and transparent conductor substrate according to claim 3, characterized in that: The volume ratio of the benzene and alcohol reagents is 100:1 to 1:100, preferably (1-5):

1.

5. The process for recycling lead and transparent conductor substrate according to claim 1, characterized in that: The benzene is at least one of toluene, chlorobenzene and xylene, preferably chlorobenzene; The ketone is acetylacetone; The alcohol reagent is at least one of ethanol, n-butanol, and isopropanol, preferably n-butanol; The ester is ethyl acetate; the ether is diethyl ether.

6. The process for recycling lead and transparent conductor substrate according to claim 1, characterized in that: The chelating agent is a carboxylic acid compound, polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, or polyamine; preferably a carboxylic acid compound; and the concentration of the chelating agent solution is 0-10 mol / L.

7. The process for recycling lead and transparent conductor substrate according to claim 6, characterized in that: The carboxylic acid compound is at least one of formic acid, acetic acid, citric acid, malic acid, tartaric acid and lactic acid.

8. The process for recycling lead and transparent conductor substrate according to claim 1, characterized in that: The solvent of the carboxylic acid compound solution is at least one of chlorobenzene, ethanol and diethyl ether.

9. A battery obtained by the process for recycling lead and a transparent conductor substrate according to any one of claims 1 to 8.

10. Use of the process for recycling lead and transparent conductor substrate according to any one of claims 1 to 8 in battery preparation.

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