Method for recovering metal lead in perovskite assembly

Abstract

The invention relates to the technical field of photovoltaics, in particular to a method for recovering metal lead in a perovskite component, which comprises the following steps: crushing the perovskite component to be recovered into a size of 2-3cm, soaking in a recovery solution, fully stirring and filtering to obtain a first filtrate; standing the first filtrate, and separating to obtain a second filtrate; adding alkali liquor into the second filtrate until lead ions in the second filtrate are completely precipitated, and filtering to obtain lead hydroxide precipitate and third filtrate; adding a silver nitrate solution into the third filtrate, and filtering to obtain a silver halide precipitate; and washing the obtained lead hydroxide precipitate with deionized water to be neutral, completely dissolving the lead hydroxide precipitate with an acid solution to obtain a high-purity lead-containing solution, carrying out halogen replacement with potassium iodide to obtain a lead iodide precipitate, filtering and drying the lead iodide precipitate, and reusing the lead iodide precipitate for preparing a perovskite solution. According to the method, the use of a large amount of organic solvent is reduced, the method is more environment-friendly, the health of workers is not harmed, the recycled lead iodide is reused for preparing the perovskite solution, and the method has higher economic value.

Description

Technical Field

[0001] The invention relates to the field of photovoltaic technology, and in particular to a method for recovering metallic lead in a perovskite component. Background Art

[0002] Perovskite solar cells are solar cells that use perovskite-type organic metal halide semiconductors as light-absorbing materials and belong to the third generation of solar cells. Metal halide perovskite materials have become promising candidate materials for third-generation solar cells and have developed very rapidly. Compared with the current commercial silicon-based and thin-film photovoltaic technologies, they have the advantages of adjustable band gap, strong absorption, high power conversion efficiency and low cost, so they are highly competitive. However, commercial products will inevitably lead to a lot of waste and scrapped equipment, and lead is an indispensable material for perovskite solar cells. It is a well-known toxic substance that can induce heavy metal poisoning through the gastrointestinal tract, respiratory tract, skin and other routes. Therefore, if perovskite components can be recycled, it will not only reduce heavy metal emissions, but also have high economic value.

[0003] After searching, the invention patent with Chinese patent publication number CN114798680A discloses a method for recycling lead halide perovskite solar cells, including: providing a lead halide perovskite solar cell to be processed, wherein the lead halide perovskite solar cell to be processed includes a cover plate and a back plate arranged opposite to each other, and a metal electrode layer and a core layer located between the cover plate and the back plate, the core layer includes an electron transport layer, a perovskite layer and a hole transport layer, and the polar solvent for recycling lead is DMF or DMSO or DMAc or GLB or NMP.

[0004] The invention patent with Chinese patent publication number CN108823414A discloses a method for recycling waste perovskite solar cells, including: immersing the perovskite solar cell in a solvent that can dissolve the perovskite material and is insoluble in other components for cleaning; performing solid-liquid separation on the cleaning liquid to obtain a lead-containing leaching liquid; reacting the obtained lead-containing leaching liquid with ammonia water to obtain a first turbid liquid; performing solid-liquid separation on the obtained turbid liquid to obtain a first solid; reacting the obtained first solid with acetic acid to obtain a second turbid liquid; performing solid-liquid separation on the second turbid liquid to obtain lead acetate solid. In this method, the cleaning solvent is at least one of N,N-dimethylformamide, dimethyl sulfoxide, and γ-butyrolactone.

[0005] The cleaning solvents in the above methods all use a large amount of toxic organic solvents, which not only harm the environment but also affect the health of the workers. In view of this, we propose a method for recovering metallic lead in perovskite components. Summary of the invention

[0006] The object of the present invention is to provide a method for recovering metallic lead in a perovskite component to solve the problems raised in the above background technology.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A method for recovering metallic lead in a perovskite component comprises the following steps:

[0009] S1. crush the perovskite component to be recycled into 2-3 cm in size, immerse it in a recovery solution, stir it thoroughly and filter it to obtain a first filtrate;

[0010] S2, fully shaking the obtained first filtrate and then standing it for liquid separation, removing the organic phase to obtain a second filtrate;

[0011] S3, adding alkali solution to the second filtrate until the lead ions in the second filtrate are completely precipitated, and filtering to obtain lead hydroxide precipitate and a third filtrate;

[0012] S4, adding silver nitrate solution to the third filtrate until the precipitation is complete, filtering to obtain silver halide precipitate, and separating the halogen of the perovskite component;

[0013] S5. After washing the lead hydroxide precipitate obtained in step S3 with deionized water until it is neutral, it is completely dissolved with acid solution to obtain a high-purity lead-containing solution, and the obtained lead-containing solution is halogen-displaced with potassium iodide to obtain a lead iodide precipitate, which is filtered and dried and can be reused to prepare a perovskite solution.

[0014] Preferably, in step S1, the perovskite component to be recycled is a perovskite light-absorbing layer of a solar cell.

[0015] Preferably, in step S1, the recovery solution includes at least one of nitric acid and acetic acid, the concentration of the recovery solution is 0.5-5 mol / L, and the weight ratio of the added amount of the recovery solution to the perovskite solar cell to be recovered is 0.1-1 mL: 1 g.

[0016] Preferably, in step S2, the oscillation includes forward rotation at 50-200 rpm / min for 5-15 min, reverse rotation at 50-200 rpm / min for 5-15 min, and the standing time is 10-30 min.

[0017] Preferably, the alkali solution in step S3 is any one of ammonia water, sodium hydroxide and potassium hydroxide, the concentration of the alkali solution is 2-8 mol / L, and the volume ratio of the added alkali solution to the second filtrate is 1-5:10.

[0018] Preferably, the concentration of the silver nitrate solution in step S4 is 0.5-4 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 1-5:30.

[0019] Preferably, the acid solution in step S5 is nitric acid or acetic acid solution, the concentration of the acid solution is 0.5-5 mol / L, and the concentration of potassium iodide is 0.5-5 mol / L.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. In the method for recovering metallic lead in the perovskite component, nitric acid or acetic acid is used as the recovery solvent to recover the perovskite component. The subsequent treatment is simple, the energy consumption is low, and the use of a large amount of organic solvents is reduced, which is more environmentally friendly and will not harm the health of workers.

[0022] 2. The method for recovering metallic lead in the perovskite component has high recovery efficiency, and the recovered lead-containing solution can be reused in preparing the perovskite solution, which has high economic value.

[0023] 3. The method for recovering metallic lead in the perovskite component separates the halogens in the third filtrate, thereby preventing the halogens from spreading into the food chain and reducing the harm of the halogens to the human body. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic flow chart of the method for recovering metallic lead in the perovskite component of the present invention. DETAILED DESCRIPTION

[0025] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] A method for recovering metallic lead in a perovskite component comprises the following steps:

[0028] S1. The perovskite component to be recycled is broken into 2-3 cm in size, immersed in a recycling solution, fully stirred and filtered to obtain a first filtrate, wherein the recycling solution is nitric acid, the concentration of the recycling solution is 0.5 mol / L, and the weight ratio of the added amount of the recycling solution to the perovskite solar cell to be recycled is 0.1 mL: 1 g. The perovskite component to be recycled is the perovskite light-absorbing layer of the solar cell. The substrate that is insoluble in the recycling solution after filtration is rinsed with deionized water and then recycled;

[0029] S2, the obtained first filtrate was fully shaken and then allowed to stand for liquid separation, the shaking included 50 rpm / min forward rotation for 15 min and 50 rpm / min reverse rotation for 15 min, and the standing time was 10 min, and the organic phase was removed to obtain a second filtrate;

[0030] S3, adding ammonia water to the second filtrate, the concentration of the ammonia water is 2 mol / L, the volume ratio of the added ammonia water to the second filtrate is 5:10, until the lead ions in the second filtrate are completely precipitated, and filtering to obtain lead hydroxide precipitate and the third filtrate;

[0031] S4, adding a silver nitrate solution to the third filtrate, wherein the concentration of the silver nitrate solution is 0.5 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 5:30, filtering to obtain a silver halide precipitate, and separating the halogen of the perovskite component;

[0032] S5. The lead hydroxide precipitate obtained in step S3 is washed with deionized water until it is neutral, and then completely dissolved with a nitric acid solution with a concentration of 0.5 mol / L to obtain a lead nitrate solution. The obtained lead nitrate solution is halogen-substituted with 0.5 mol / L potassium iodide to obtain a lead iodide precipitate with a purity of 99.91%. The lead iodide precipitate is filtered and dried, and can be reused to prepare a perovskite solution.

[0033] Example 2

[0034] A method for recovering metallic lead in a perovskite component comprises the following steps:

[0035] S1. The perovskite component to be recycled is broken into 2-3 cm in size, immersed in a recycling solution, fully stirred and filtered to obtain a first filtrate, the recycling solution is nitric acid, the concentration of the recycling solution is 1 mol / L, the weight ratio of the added amount of the recycling solution to the perovskite solar cell to be recycled is 0.3 mL: 1 g, the perovskite component to be recycled is the perovskite light-absorbing layer of the solar cell, and the substrate that is insoluble in the recycling solution after filtration is rinsed with deionized water and then recycled;

[0036] S2, the obtained first filtrate was fully shaken and then allowed to stand for separation, the shaking included 100 rpm / min forward rotation for 10 min and 100 rpm / min reverse rotation for 10 min, and the standing time was 15 min, and the organic phase was removed to obtain a second filtrate;

[0037] S3, adding ammonia water to the second filtrate, the concentration of the ammonia water is 4 mol / L, the volume ratio of the added ammonia water to the second filtrate is 3:10, until the lead ions in the second filtrate are completely precipitated, and filtering to obtain lead hydroxide precipitate and the third filtrate;

[0038] S4, adding a silver nitrate solution to the third filtrate, wherein the concentration of the silver nitrate solution is 1 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 4:30, filtering to obtain a silver halide precipitate, and separating the halogen of the perovskite component;

[0039] S5. The lead hydroxide precipitate obtained in step S3 is washed with deionized water until it is neutral, and then completely dissolved with a nitric acid solution with a concentration of 1 mol / L to obtain a lead nitrate solution. The obtained lead nitrate solution is halogen-substituted with 1 mol / L potassium iodide to obtain a lead iodide precipitate with a purity of 99.93%. The lead iodide precipitate is filtered and dried, and can be reused to prepare a perovskite solution.

[0040] Example 3

[0041] A method for recovering metallic lead in a perovskite component comprises the following steps:

[0042] S1. The perovskite component to be recycled is broken into 2-3 cm in size, immersed in a recycling solution, fully stirred and filtered to obtain a first filtrate, wherein the recycling solution is acetic acid, the concentration of the recycling solution is 2 mol / L, and the weight ratio of the added amount of the recycling solution to the perovskite solar cell to be recycled is 0.8 mL: 1 g. The perovskite component to be recycled is the perovskite light-absorbing layer of the solar cell. The substrate that is insoluble in the recycling solution after filtration is rinsed with deionized water and then recycled;

[0043] S2, the obtained first filtrate was fully shaken and then allowed to stand for liquid separation, the shaking included 150 rpm / min forward rotation for 12 min and 150 rpm / min reverse rotation for 12 min, and the standing time was 20 min, and the organic phase was removed to obtain a second filtrate;

[0044] S3, adding sodium hydroxide to the second filtrate, the concentration of sodium hydroxide is 6 mol / L, the volume ratio of the added sodium hydroxide to the second filtrate is 1:10, until the lead ions in the second filtrate are completely precipitated, and filtering to obtain the lead hydroxide precipitate and the third filtrate;

[0045] S4, adding a silver nitrate solution to the third filtrate, wherein the concentration of the silver nitrate solution is 2 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 2:30, filtering to obtain a silver halide precipitate, and separating the halogen of the perovskite component;

[0046] S5. The lead hydroxide precipitate obtained in step S3 is washed with deionized water until it is neutral, and then completely dissolved with an acetic acid solution having a concentration of 3 mol / L to obtain a lead acetate solution. The obtained lead acetate solution is halogen-substituted with 2 mol / L potassium iodide to obtain a lead iodide precipitate having a purity of 99.92%. The lead iodide precipitate is filtered and dried, and can be reused to prepare a perovskite solution.

[0047] Example 4

[0048] A method for recovering metallic lead in a perovskite component comprises the following steps:

[0049] S1. The perovskite component to be recycled is broken into 2-3 cm in size, immersed in a recycling solution, fully stirred and filtered to obtain a first filtrate, wherein the recycling solution is acetic acid, the concentration of the recycling solution is 5 mol / L, and the weight ratio of the added amount of the recycling solution to the perovskite solar cell to be recycled is 1 mL: 1 g. The perovskite component to be recycled is the perovskite light-absorbing layer of the solar cell. The substrate that is insoluble in the recycling solution after filtration is rinsed with deionized water and then recycled;

[0050] S2, the obtained first filtrate was fully shaken and then allowed to stand for separation, the shaking included 200 rpm / min forward rotation for 5 min and 200 rpm / min reverse rotation for 5 min, and the standing time was 30 min, and the organic phase was removed to obtain a second filtrate;

[0051] S3, adding potassium hydroxide to the second filtrate, the concentration of potassium hydroxide is 8 mol / L, the volume ratio of the added potassium hydroxide to the second filtrate is 1:10, until the lead ions in the second filtrate are completely precipitated, and filtering to obtain the lead hydroxide precipitate and the third filtrate;

[0052] S4, adding a silver nitrate solution to the third filtrate, wherein the concentration of the silver nitrate solution is 4 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 1:30, filtering to obtain a silver halide precipitate, and separating the halogen of the perovskite component;

[0053] S5. The lead hydroxide precipitate obtained in step S3 is washed with deionized water until it is neutral, and then completely dissolved with an acetic acid solution having a concentration of 5 mol / L to obtain a lead acetate solution. The obtained lead acetate solution is halogen-displaced with 5 mol / L potassium iodide to obtain a lead iodide precipitate having a purity of 99.94%. The lead iodide precipitate is filtered and dried, and can be reused to prepare a perovskite solution.

[0054] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions are only preferred examples of the present invention and are not intended to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for recovering metallic lead in a perovskite component, characterized in that: The following steps are involved: S1. crush the perovskite component to be recycled into 2-3 cm in size, immerse it in a recycling solution, stir it thoroughly and filter it to obtain a first filtrate; S2, fully shaking the obtained first filtrate and then standing it for liquid separation, removing the organic phase to obtain a second filtrate; S3, adding alkali solution to the second filtrate until the lead ions in the second filtrate are completely precipitated, and filtering to obtain lead hydroxide precipitate and a third filtrate; S4, adding silver nitrate solution to the third filtrate until the precipitation is complete, filtering to obtain silver halide precipitate, and separating the halogen of the perovskite component; S5. After washing the lead hydroxide precipitate obtained in step S3 with deionized water until it is neutral, it is completely dissolved with acid solution to obtain a high-purity lead-containing solution, and the obtained lead-containing solution is halogen-displaced with potassium iodide to obtain a lead iodide precipitate, which is filtered and dried and can be reused to prepare a perovskite solution.

2. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: In the step S1, the perovskite component to be recycled is the perovskite light-absorbing layer of the solar cell.

3. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: In the step S1, the recovery solution includes at least one of nitric acid and acetic acid, the concentration of the recovery solution is 0.5-5 mol / L, and the weight ratio of the added amount of the recovery solution to the perovskite solar cell to be recovered is 0.1-1 mL: 1 g.

4. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: In the step S2, the oscillation includes forward rotation at 50-200 rpm / min for 5-15 min, reverse rotation at 50-200 rpm / min for 5-15 min, and a standing time of 10-30 min.

5. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: In step S3, the alkali solution is any one of ammonia water, sodium hydroxide and potassium hydroxide, the concentration of the alkali solution is 2-8 mol / L, and the volume ratio of the added alkali solution to the second filtrate is 1-5:

10.

6. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: The concentration of the silver nitrate solution in step S4 is 0.5-4 mol / L, and the volume ratio of the added silver nitrate solution to the third filtrate is 1-5:

30.

7. The method for recovering metallic lead in a perovskite component according to claim 1, characterized in that: In step S5, the acid solution is nitric acid or acetic acid solution, the concentration of the acid solution is 0.5-5 mol / L, and the concentration of potassium iodide is 0.5-5 mol / L.

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