Method for recycling and utilization of lead halide in perovskite solar cell

Abstract

The present invention relates to a method for recovering and utilizing lead halide from perovskite solar cells. The perovskite solar cells to be recovered are placed in a heating device and heated at a high temperature to remove the low-boiling-point materials in the perovskite solar cells, leaving the high-boiling-point materials. The remaining high-boiling-point materials are immersed in a solvent, and a lead-containing solution is obtained after filtration. A complexing agent is added to the lead-containing solution for complexation reaction, and a high-purity lead-containing complex is obtained after the filter cake is dried. The recovered lead-containing complex is dissolved and formulated into a coating solution, and then the coating solution is coated on the prepared perovskite absorption layer and dried to obtain a lead complex passivation layer. Then, a second transport layer and a back electrode are successively prepared on the lead complex passivation layer until the manufacturing process of the perovskite solar cell is completed. The process of the present invention is simple, which can not only recover and utilize the lead-containing components in the waste perovskite solar cell materials, but also improve the performance of the newly prepared perovskite solar cells.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a method for recovering and utilizing lead halide in perovskite solar cells. Background Art

[0002] Due to the advantages of low preparation cost, simple process route, and wide raw material sources of perovskite solar cells, their industrial development has been greatly promoted. However, in industrial production, the heavy metal lead in waste perovskite solar cells will cause irreversible harm to the environment and human body, and at the same time, it will also cause waste of resources. Therefore, it is particularly important to provide a method for recycling and utilizing lead in waste perovskite solar cells.

[0003] There are few existing lead recovery technologies for perovskite solar cells, and most of them use multi-step solution separation methods to recover the materials of each layer of perovskite solar cells, which will result in impure recovered lead iodide and require secondary purification before it can be reused. At the same time, different perovskite solar cells need to screen different separation agents for separation and recovery, which not only lacks universality but also increases the recovery cost. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for recovering and utilizing lead halide in perovskite solar cells, which has a simple process and can not only recover and utilize the lead-containing components in the materials of waste perovskite solar cells but also improve the performance of newly prepared perovskite solar cells.

[0005] The present invention is realized as follows. A method for recovering lead halide in perovskite solar cells is provided, including the following steps:

[0006] Step 1: Put the perovskite solar cell to be recycled into a heating device and heat it at a high temperature to remove the low-boiling-point materials in the perovskite solar cell, leaving the high-boiling-point materials;

[0007] Step 2: Immerse the remaining high-boiling-point materials in a solvent, and filter to obtain a lead-containing solution;

[0008] Step 3: Add a complexing agent to the lead-containing solution for complexation reaction, and dry the filtrate to obtain a high-purity lead-containing complex, realizing the recovery of lead halide materials from the perovskite solar cell to be recycled;

[0009] Among them, in the perovskite solar cell, there is a perovskite layer, and in the perovskite layer, there is a preparation material with a molecular structural formula of APbX3 containing lead halide. In the formula, A is at least one of cesium, rubidium, amino group, amidino group, and alkali group, and X is at least one of halogen elements.

[0010] Furthermore, in step 2, the solvent is any one of acetone, acetonitrile, dimethyl sulfoxide (DMSO), γ-butyrolactone and dimethylformamide (DMF).

[0011] Furthermore, in step three, the complexing agent is any one of cyclic carboxyl-containing ligands and their derivatives, cyclic hydrazide ligands and their derivatives, and o-benzoquinone ligands and their derivatives.

[0012] Furthermore, the complexing agent is any one of 3,4-pyridinedicarboxylic acid, 2,5-di-tert-butylhydroquinone and 2,6-pyridinedicarboxylic acid hydrazone.

[0013] Furthermore, in step three, the preparation method of the lead-containing complex is a solution method or a hydrothermal method.

[0014] The present invention is implemented by providing a method for preparing a perovskite solar cell using a lead-containing complex recovered by the lead halide recovery method of the perovskite solar cell as described above. The internal structure of the perovskite solar cell includes a transparent conductive electrode, a first transmission layer, a perovskite light absorption layer, a lead complex passivation layer, a second transmission layer and a back electrode from bottom to top. The preparation method of the perovskite solar cell includes the following steps:

[0015] The recovered lead-containing complex is dissolved and prepared into a coating liquid, which is then coated on the prepared perovskite absorption layer and dried to obtain a lead complex passivation layer. A second transmission layer and a back electrode are then sequentially prepared on the lead complex passivation layer until the production process of the perovskite solar cell is completed.

[0016] Furthermore, the method of dissolving the lead-containing complex into a coating liquid comprises: dissolving the lead-containing complex in a coating solvent and stirring sufficiently to obtain a coating liquid; wherein the coating solvent comprises any one of chlorobenzene, anisole, ethyl acetate and tetrahydrofuran.

[0017] Furthermore, the coating method of the coating liquid includes any one of printing, scraping and spin coating.

[0018] Compared with the prior art, the method for recovering lead halide from a perovskite solar cell and its utilization method of the present invention utilize the thermal decomposition characteristics of the perovskite absorption layer material, the selective solubility of lead halide, and the highly selective coordination property of the complexing agent. First, the waste perovskite solar cell is heated at a high temperature to remove low-boiling materials such as halogenated organic cations, leaving high-boiling materials containing components such as lead. Then, the obtained high-boiling materials are put into a solvent to obtain a lead-rich solution. After that, the complexing agent is used to enrich lead to obtain a high-purity lead complex, which can act as a passivation layer in the perovskite solar cell to effectively passivate and repair the defects on the surface and grain boundaries of the perovskite thin film. The method of the present invention has a simple process, can not only recycle the lead-containing components in the waste perovskite solar cell materials, but also improve the performance of the newly prepared perovskite solar cell. Detailed implementation manners

[0019] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0020] A preferred embodiment of the method for recovering lead halide from a perovskite solar cell of the present invention includes the following steps:

[0021] Step 1: Put the perovskite solar cell to be recycled into a heating device and heat it at a high temperature to remove the low-boiling materials in the perovskite solar cell, leaving high-boiling materials.

[0022] Step 2: Immerse the remaining high-boiling materials in a solvent, and filter to obtain a lead-containing solution.

[0023] Step 3: Add a complexing agent to the lead-containing solution for a complexation reaction, and dry the filtrate to obtain a high-purity lead complex, realizing the recovery of lead halide materials from the perovskite solar cell to be recycled.

[0024] Among them, in the perovskite solar cell, there is a perovskite layer, and in the perovskite layer, there is a preparation material with a molecular structure formula of APbX3 containing lead halide. In the formula, A is at least one of cesium, rubidium, amino group, amidino group, and alkali metal group, and X is at least one of halogen elements.

[0025] Specifically, in Step 2, the solvent is any one of acetone, acetonitrile, dimethyl sulfoxide (DMSO), γ-butyrolactone, and dimethylformamide (DMF).

[0026] Specifically, in Step 3, the complexing agent is any one of cyclic carboxyl-containing ligands and their derivatives, cyclic hydrazide-containing ligands and their derivatives, and o-benzoquinone-containing ligands and their derivatives.

[0027] Specifically, the complexing agent is any one of 3,4-pyridinedicarboxylic acid, 2,5-di-tert-butylhydroquinone, and 2,6-pyridinedicarboxylic hydrazide m-hydroxybenzaldehyde hydrazone.

[0028] Specifically, in step three, the preparation method of the lead-containing complex is the solution method or the hydrothermal method.

[0029] The present invention also discloses a method for preparing a perovskite solar cell using a lead-containing complex recovered by the method for recovering lead halide of the perovskite solar cell as described above. The internal structure of the perovskite solar cell sequentially includes a transparent conductive electrode, a first transport layer, a perovskite light-absorbing layer, a lead complex passivation layer, a second transport layer, and a back electrode from bottom to top. The preparation method of the perovskite solar cell includes the following steps:

[0030] Dissolve the recovered lead-containing complex to prepare a coating solution, then coat the coating solution on the prepared perovskite absorption layer and dry it to obtain a lead complex passivation layer, and then sequentially prepare a second transport layer and a back electrode on the lead complex passivation layer until the manufacturing process of the perovskite solar cell is completed.

[0031] Specifically, the method for dissolving the lead-containing complex to prepare a coating solution includes: dissolving the lead-containing complex in a coating solvent and stirring well to obtain a coating solution; wherein, the coating solvent is any one of polar solvents such as chlorobenzene, anisole, ethyl acetate, and tetrahydrofuran.

[0032] Specifically, the coating method of the coating solution includes any one of printing, doctor blading, and spin coating.

[0033] Specifically, the preparation material of the transparent conductive substrate is any one of indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), or fluorine-doped tin oxide (FTO).

[0034] Specifically, the first transport layer can be a hole transport layer or an electron transport layer. Correspondingly, the second transport layer can be a hole transport layer or an electron transport layer. Among them, the preparation materials of the hole transport layer can be at least one of tetraphenylbenzidine derivatives, BTCV polymers, NiO x , V2O5, PEDOT:PSS, CuI, CuO, CuSCN, PVK:TFB thin films, and Spiro-OMeTAD. The preparation materials of the electron transport layer can be at least one of C60, PCBM, SnO2, PCBM, TiO2, ZnO, and ZnO-ZnS.

[0035] Specifically, the preparation material of the back electrode is any one of silver, copper, gold, aluminum, and transparent conductive electrodes.

[0036] The following further illustrates the method for recovering lead halide and its utilization method of the perovskite solar cell of the present invention through specific embodiments.

[0037] Example 1

[0038] The first example of the method for recovering lead halide and its utilization method of the perovskite solar cell of the present invention includes the following steps:

[0039] (11) Removal of low-boiling-point materials: Put the waste methylammonium lead iodide (MAPbI3) perovskite solar cell module to be recycled into a muffle furnace and heat it at 300 °C for 2 h. Low-boiling-point materials in the solar cell, such as MAI, etc., will decompose and be removed in the form of gas, leaving only high-boiling-point solids such as lead iodide (PbI2) and gold (Au) electrodes.

[0040] (12) Enrichment of lead: Immerse the high-boiling-point solid in DMSO solvent for 1 h and then take it out to obtain a lead-containing suspension. After high-speed centrifugation of the suspension, a lead-rich solution A1 is obtained.

[0041] (13) Preparation of lead complex: Add 3,4-pyridinedicarboxylic acid (3,4-pdc) and triethylamine to water according to the stoichiometric ratio of 1:2 and stir to dissolve to obtain solution B1 and solution C1. Then pour solution B1 into solution A1 and stir for 20 min to obtain a mixed solution D1. Then add solution C1 to solution D1 while stirring and stir for half an hour, and then let it stand for 10 min to obtain a turbid solution containing lead complex. Filter the above turbid solution and wash it 3 times with deionized water to obtain 3,4-pyridinedicarboxylic acid lead (Pb(3,4-pdc)) solid. After drying, a Pb(3,4-pdc) lead complex material is obtained.

[0042] (14) Preparation of a new perovskite solar cell and use of the lead complex passivation layer:

[0043] (141) Prepare a hole transport layer PTAA and a perovskite absorption layer MAPbI3 on an ITO transparent conductive substrate in sequence, and then spin-coat a coating solution of Pb(3,4-pdc) lead complex on the perovskite absorption layer: Spin-coat a 50 mg / mL chloroform suspension of Pb(3,4-pdc) on the perovskite absorption layer MAPbI3 at a speed of 3000 rpm / s for 30 s, and then anneal it at 100 °C for 10 min to obtain a Pb(3,4-pdc) lead complex passivation layer.

[0044] (142) Prepare an electron transport layer PCBM and a back electrode Au on the Pb(3,4-pdc) lead complex passivation layer in sequence to complete the preparation of the perovskite solar cell.

[0045] Example 2

[0046] Example of the method for recovering lead halide and its utilization method for the second perovskite solar cell of the present invention, including the following steps:

[0047] (21) Removal of low-boiling-point materials: Put the waste formamidinium lead iodide (FAPbI3) perovskite solar cell module into a muffle furnace and heat it at 300 °C for 2 h. Low-boiling-point materials in the solar cell such as FAI will decompose and be removed in the form of gas, leaving only high-boiling-point solids such as lead iodide (PbI2) and CuO produced by the oxidation of the Cu electrode.

[0048] (22) Enrichment of lead: Immerse the high-boiling-point solid in DMF solvent for 1 h and then take it out to obtain a lead-containing suspension. After high-speed centrifugation of the suspension, a lead-rich solution A2 is obtained.

[0049] (23) Preparation of lead complex: Add 5-hydroxy-1,3-benzenedicarboxylic acid (H2bmbdc) to water and stir to dissolve to obtain solution B. Then pour solution B2 into solution A2 and stir for 20 min to obtain a lead complex precursor solution C2. Then load the precursor solution C2 into a polytetrafluoroethylene high-pressure reaction kettle and seal it. Subsequently, put the reaction kettle into an oven and react at 170 °C for 24 h, and then take it out and cool it. Finally, centrifuge the reacted turbid solution at a speed of 10000 rpm / min for 10 min to obtain a solid precipitate, and rinse the precipitate 3 times with deionized water and dry it to obtain a 5-hydroxy-1,3-benzenedicarboxylic acid lead (Pb(bmbdc)) lead complex solid material.

[0050] (24) Preparation of a new perovskite solar cell and use of a lead complex passivation layer:

[0051] (241) Prepare an electron transport layer SnO2 and a perovskite absorption layer FAPbI3 on an ITO transparent conductive substrate in sequence, and then scrape a coating solution containing Pb(bmbdc) on the perovskite absorption layer: Use the scraping method to scrape a 50 mg / mL Pb(bmbdc) anisole suspension onto the perovskite absorption layer FAPbI3, and then anneal it at 100 °C for 10 min to obtain a Pb(bmbdc) lead complex passivation layer.

[0052] (242) Prepare a hole transport layer NiO and a back electrode Ag on the Pb(bmbdc) lead complex passivation layer in sequence to complete the preparation of the perovskite solar cell. x And complete the preparation of the perovskite solar cell.

[0053] The above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for recovering lead halide from a perovskite solar cell, characterized in that, The steps include: Step 1: Place the perovskite solar cell to be recycled in a heating device and heat it at high temperature to remove the low boiling point materials in the perovskite solar cell and leave the high boiling point materials; Step 2, soaking the remaining high boiling point material in a solvent, and filtering to obtain a lead-containing solution; Step 3, adding a complexing agent to the lead-containing solution to carry out a complexing reaction, and obtaining a high-purity lead-containing complex after drying the filtered product, thereby realizing the recovery of lead halide materials from the perovskite solar cell to be recovered; The perovskite solar cell includes a perovskite layer, and the perovskite layer includes a preparation material containing lead halide and having a molecular structure of APbX3, wherein A is at least one of cesium, rubidium, amine, amidine, and alkali, and X is at least one of halogen elements; In step three, the complexing agent is any one of a cyclic carboxyl-containing ligand, a cyclic hydrazide ligand, and an o-benzoquinone ligand.

2. The method for recovering lead halide of the perovskite solar cell according to claim 1, wherein In step 2, the solvent is any one of acetone, acetonitrile, dimethyl sulfoxide (DMSO), γ-butyrolactone and dimethylformamide (DMF).

3. The method for recovering lead halide of the perovskite solar cell according to claim 1, characterized in that, The complexing agent is any one of 3,4-pyridinedicarboxylic acid, 2,5-di-tert-butylhydroquinone and 2,6-pyridinedicarboxylic acid hydrazone.

4. The method for recovering lead halide of the perovskite solar cell according to claim 1, characterized in that, In step three, the preparation method of the lead-containing complex is a solution method or a hydrothermal method.

5. A method for preparing a perovskite solar cell using a lead-containing complex recovered by a method for recovering lead halide of a perovskite solar cell according to any one of claims 1 to 4, characterized in that, The internal structure of the perovskite solar cell includes, from bottom to top, a transparent conductive electrode, a first transmission layer, a perovskite light absorption layer, a lead complex passivation layer, a second transmission layer, and a back electrode. The preparation method of the perovskite solar cell includes the following steps: The recovered lead-containing complex is dissolved and prepared into a coating liquid, which is then coated on the prepared perovskite light-absorbing layer and dried to obtain a lead complex passivation layer. A second transmission layer and a back electrode are then sequentially prepared on the lead complex passivation layer until the production process of the perovskite solar cell is completed.

6. The utilization method according to claim 5, wherein The method for dissolving the lead-containing complex to prepare a coating liquid comprises: dissolving the lead-containing complex in a coating solvent and stirring it fully to obtain the coating liquid; wherein the coating solvent comprises any one of chlorobenzene, anisole, ethyl acetate and tetrahydrofuran.

7. The utilization method according to claim 5, characterized in that, The coating method of the coating liquid includes any one of printing, scraping and spin coating.