阅读说明：本技术 一种钙钛矿器件材料的回收方法 (Method for recovering perovskite device material ) 是由 何祝兵 冯溪渊 于 2020-12-08 设计创作，主要内容包括：本发明提供了一种钙钛矿器件材料的回收方法,所述回收方法包括以下步骤：(1)将钙钛矿器件用胺的醇溶液处理,得到导电基材与第一处理溶液,回收导电基材并加热蒸发第一处理溶液,得到钙钛矿-功能材料混合物；(2)将步骤(1)得到的钙钛矿-功能材料混合物用溶剂处理,之后离心,得到含金属产物与第二处理溶液,将第二处理溶液加热蒸发,得到并回收功能材料；(3)将步骤(2)得到的含金属产物用醇溶解,离心分离得到卤化金属和第三处理溶液,将第三处理溶液加热蒸发,得到并回收有机盐；本发明提供的回收方法安全环保,操作简单,对钙钛矿器件中所有功能材料均可回收,并能循环利用溶剂,最大化地实现无害化处理。(The invention provides a recycling method of a perovskite device material, which comprises the following steps: (1) treating the perovskite device with an amine alcoholic solution to obtain a conductive base material and a first treatment solution, recovering the conductive base material and heating to evaporate the first treatment solution to obtain a perovskite-functional material mixture; (2) treating the perovskite-functional material mixture obtained in the step (1) with a solvent, centrifuging to obtain a metal-containing product and a second treatment solution, and heating and evaporating the second treatment solution to obtain and recover a functional material; (3) dissolving the metal-containing product obtained in the step (2) with alcohol, performing centrifugal separation to obtain halogenated metal and a third treatment solution, heating and evaporating the third treatment solution to obtain and recover organic salt; the recovery method provided by the invention is safe and environment-friendly, is simple to operate, can recover all functional materials in the perovskite device, can recycle the solvent, and maximally realizes harmless treatment.)

1. A method of recycling perovskite device material, the method comprising the steps of:

(1) treating the perovskite device with an amine alcoholic solution to obtain a conductive base material and a first treatment solution, recovering the conductive base material and heating to evaporate the first treatment solution to obtain a perovskite-functional material mixture;

(2) treating the perovskite-functional material mixture obtained in the step (1) with a solvent, centrifuging to obtain a metal-containing product and a second treatment solution, and heating and evaporating the second treatment solution to obtain and recover a functional material;

(3) dissolving the metal-containing product obtained in the step (2) with alcohol, performing centrifugal separation to obtain halogenated metal and a third treatment solution, heating and evaporating the third treatment solution to obtain and recover organic salt;

the perovskite having AMX₃The compound is represented by a general formula, wherein M is a central metal cation, X is an anion, the central metal cation M and the anion X form a coordination octahedral structure, A exists in an octahedral gap, and A is selected from any one or a combination of at least two of halide, Cs or Rb of organic amine.

2. The method of recycling a perovskite device material as claimed in claim 1, wherein the M is selected from any one or a combination of at least two of Ge, Sn, Pb, Cu, Mn, Sb or Bi ions;

the X is selected from any one or combination of at least two of Cl, Br or I ions;

preferably, the halide salt of an organic amine comprises CH₃NH₃I(MAI)、HN＝CHNH₃Any one or the combination of at least two of I (FAI), butylamine iodine or oleylamine iodine;

preferably, the functional material comprises PCBM and derivatives thereof, any one or a combination of at least two of P3HT, C60, C70, Spiro-OMeTAD, X60, X55, PTAA, Poly-TPD or PTAA-2 Me;

preferably, the organic salt comprises any one of or a combination of at least two of a chloride salt of the amine, a bromide salt of the amine, or an iodide salt of the amine.

3. A method of recycling a perovskite device material as claimed in claim 1 or 2, wherein the perovskite device comprises any one of a solar cell, LED or field effect transistor comprising a perovskite material.

4. The method for recycling perovskite device material as claimed in any one of claims 1 to 3, wherein the amine in step (1) comprises any one or a combination of at least two of methylamine, ethylamine, propylamine or ethanolamine;

preferably, the alcohol in step (1) comprises any one of methanol, ethanol, n-propanol, isopropanol or tert-butanol or a combination of at least two thereof;

preferably, the mass fraction of the alcoholic solution of the amine in step (1) is 20-40%.

5. The process for recycling perovskite device material as claimed in any one of claims 1 to 4, wherein the temperature of the heating in step (1) is 20 to 100 ℃.

6. The method for recycling perovskite device material as claimed in any one of claims 1 to 5, wherein the solvent in step (2) comprises any one or a combination of at least two of dichloromethane, chloroform, carbon tetrachloride, toluene, n-hexane or cyclohexane;

preferably, the temperature of the heating in step (2) is 20 to 100 ℃.

7. The process for recovering a perovskite device material as claimed in any one of claims 1 to 6, wherein the alcohol in step (3) comprises any one of methanol, ethanol, n-propanol, isopropanol or tert-butanol or a combination of at least two thereof;

preferably, the temperature of the heating in step (3) is 20 to 100 ℃.

8. The method for recycling a perovskite device material as claimed in any one of claims 1 to 7, further comprising a step (4) after the obtaining and recycling of the organic salt in step (3): crystallizing the halogenated metal obtained in the step (3) as a precursor, and recovering the halogenated metal to obtain the perovskite single crystal.

9. The method for recycling perovskite device material as claimed in claim 8, wherein the temperature profile of the crystallization in step (4) is: the initial temperature is 100 ℃, and then the temperature is reduced to 60 ℃ at the cooling rate of 0.5-2 ℃/h.

10. A method of recycling a perovskite device material as claimed in any one of claims 1 to 9, wherein the recycling method comprises the steps of:

(1) treating the perovskite device with an amine alcoholic solution with the mass fraction of 20-40% to obtain a conductive base material and a first treatment solution, recovering the conductive base material, and heating and evaporating the first treatment solution at the temperature of 20-100 ℃ to obtain a perovskite-functional material mixture;

(2) treating the perovskite-functional material mixture obtained in the step (1) with a solvent, centrifuging to obtain a metal-containing product and a second treatment solution, and heating and evaporating the second treatment solution at 20-100 ℃ to obtain and recover a functional material;

(3) dissolving the metal-containing product obtained in the step (2) with alcohol, performing centrifugal separation to obtain halogenated metal and a third treatment solution, heating and evaporating the third treatment solution at the temperature of 20-100 ℃, and obtaining and recovering organic salt;

(4) crystallizing the halogenated metal obtained in the step (3) as a precursor, and recovering the halogenated metal to obtain the perovskite single crystal.

Technical Field

The invention belongs to the field of chemical industry, and particularly relates to a method for recovering a perovskite device material, in particular to a method for recovering a green, environment-friendly and sustainable perovskite device material.

Background

Photovoltaic modules must be disassembled and disposed of or reused in some way at the end of their useful life. Perovskite solar cells are an emerging solar cell technology and have attracted extensive attention in the scientific and industrial sectors. The novel perovskite-containing solar cell laboratory has continuous breakthrough in efficiency and has a good solution in the aspects of stability and large area. However, their active substances are based on soluble heavy metal compounds, and from the perspective of supervision and environmental health, the toxicity of heavy metal-containing perovskite materials per se retards the industrial development of perovskite devices. An important step after the industrialization of the perovskite device is that recycling needs to be considered, and the recycling and regeneration technology of the perovskite device proposed at present can partially solve the problem, but the schemes mainly consider recycling the perovskite, and do not consider the comprehensive recycling of other functional materials in detail. For the perovskite solar cell with low manufacturing cost, any high-cost recycling technology can prolong the investment recycling period and cannot embody the excellent performance of the perovskite solar cell. Therefore, a comprehensive recovery method of all functional materials is provided, the recovery difficulty of the device is further reduced, and the method is particularly important for the industrialization of the perovskite device.

CN107513618B discloses a lead recovery method for perovskite battery, which comprises the following steps: crushing the perovskite battery to form fragments; soaking the fragments in a soaking solution, and then carrying out solid-liquid separation to obtain a lead-containing separation solution; the soaking solution comprises an organic solvent capable of dissolving the perovskite material; and carrying out chemical precipitation operation or electrolysis operation on the lead-containing separation solution to obtain a lead-containing solid. The lead recovery method of the perovskite battery recovers lead, thereby avoiding lead pollution and being environment-friendly; on the other hand, the recycled lead is changed into valuable, and the effective utilization of resources is improved. In addition, the lead recovery method of the perovskite battery is simple and easy to implement, and can be beneficial to large-scale industrial application. But the method is not related to other recyclable materials, and wastes are caused.

CN109943728B discloses a method for recovering lead in a perovskite solar cell, which comprises: manually stripping the substrate material, the conductive glass and the top electrode; removing the hole transport layer by a chemical solvent dissolving method; extracting a lead-containing compound; and (4) detecting the lead recovery rate, the recovery quality and the recovery effect. The method solves the problem of toxicity of the perovskite solar cell material, ensures green and environment-friendly performance in the implementation process, and avoids the pollution problem in the recovery process. But the dimethyl formamide used as a solvent has high toxicity and seriously affects the environment and the human health.

CN106876597A discloses a device recycling process for degraded or abandoned perovskite solar cells, which includes a primary cleaning treatment of degraded perovskite solar cells, a thorough cleaning and treatment of obtained substrates, the use of the substrates for preparing solar cells again, a primary treatment of generated waste liquid (mixed organic solution and suspended matter or precipitate of chemical components of each functional layer) to obtain a back electrode metal material, and a further treatment of the generated waste liquid to obtain lead halide which can participate in a new round of device preparation. The wet process has the advantages of low temperature, low energy consumption and the like, can avoid potential threats to environmental ecology and human health caused by lead loss, can realize full and reutilization of resources, has potential good economic benefits, and can further promote the practicability of the cheap perovskite solar cell. But also due to the environmental impact involved in the use of dimethylformamide.

The recycling of perovskite is an important part for the industrialization of perovskite devices, and the problem of incomplete recycling of functional materials of perovskite devices exists at present. Therefore, how to provide a comprehensive recovery method for all functional materials of the perovskite device becomes a problem to be solved urgently.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a method for recovering a perovskite device material, and particularly provides a method for recovering a perovskite device material which is green, environment-friendly and sustainable. The recovery method provided by the invention is safe and environment-friendly, is simple to operate, can recover all functional materials in the perovskite device, can recycle the solvent, and maximally realizes harmless treatment.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a recycling method of a perovskite device material, which comprises the following steps:

(1) treating the perovskite device with an amine alcoholic solution to obtain a conductive base material and a first treatment solution, recovering the conductive base material and heating to evaporate the first treatment solution to obtain a perovskite-functional material mixture;

(2) treating the perovskite-functional material mixture obtained in the step (1) with a solvent, centrifuging to obtain a metal-containing product and a second treatment solution, and heating and evaporating the second treatment solution to obtain and recover a functional material;

(3) and (3) dissolving the metal-containing product obtained in the step (2) with alcohol, performing centrifugal separation to obtain metal halide and a third treatment solution, and heating and evaporating the third treatment solution to obtain and recover organic salt.

The perovskite having AMX₃The compound is represented by the general formula (I), wherein M is a central metal cation, X is an anion, the central metal cation M and the anion X form a coordination octahedral structure, A exists in an octahedral gap, and A is selected from any one or a combination of at least two of organic amine halide, Cs or Rb, such as organic amine halide and Cs combination, Cs and Rb combination or organic amine halide and Rb combination, but not limited to the listed combinations, and other combinations not listed in the above combination range are also applicable. The conductive substrate includes a conductive base and/or a metal electrode.

The recovery method is safe and environment-friendly, is simple to operate, can recover all the component materials in the perovskite device, greatly reduces the material waste and the manufacturing cost of the perovskite device, can recycle the solvent, and maximally realizes harmless treatment.

Preferably, the M is selected from any one or a combination of at least two of Ge, Sn, Pb, Cu, Mn, Sb or Bi ions, such as Ge and Sn ions, Sn and Pb ions, Pb and Bi ions, and the like, but is not limited to the combinations listed above, and other combinations not listed above within the respective combinations listed above are also applicable.

The X is selected from any one or a combination of at least two of Cl, Br or I ions, such as a combination of Cl and Br ions, a combination of Br and I ions or a combination of Cl and I ions, and the like, but is not limited to the listed combinations, and other combinations not listed in the above combination range are also applicable.

Preferably, the first and second electrodes are formed of a metal,the halide salt of the organic amine comprises CH₃NH₃I(MAI)、HN＝CHNH₃Any one or combination of at least two of I (FAI), butylamine iodine or oleylamine iodine, e.g. CH₃NH₃I (MAI) and HN ═ CHNH₃Combination of I (FAI), combination of butylamine iodide and oleylamine iodide or butylamine iodide and CH₃NH₃Combinations of I and MAI, but not limited to the combinations listed above, and other combinations not listed above within the scope of each combination are also applicable.

Preferably, the functional material comprises [6,6] -phenyl-C61-methyl butyrate (PCBM) and derivatives thereof, poly (3-hexylthiophene-2, 5-diyl) (P3HT), fullerene C60(C60), fullerene C70(C70), 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-ome tad), N2, N2, N2', N2', N7, N7, N7', N7' -octa (4-methoxyphenyl) Spiro [ fluorene-9, 9' -xanthene ] -2,2',7,7' -tetramine (X60), N2, N7-bis (4-methoxyphenyl) -N2, N7-bis (2-Spiro [ fluorene-9, 9' -xanthene ]) -Spiro [ fluorene-9), 9' -xanthene ] -2, 7-diamine (X55), Poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), Poly [ bis (4-phenyl) (4-butylphenyl) amine ] (Poly-TPD) or Poly [ bis (4-phenyl) (2, 4-dimethylphenyl) amine ] (PTAA-2Me), for example, a combination of C60 and C70, a combination of PCBM and P3HT or a combination of X60 and PCBM, but not limited to the combinations listed, and other combinations not listed within the above-mentioned combinations are also applicable.

The derivative of PCBM may be, for example, [6,6] -phenyl C61 methyl butyrate (PC61BM) or [6,6] -phenyl C71 methyl butyrate.

Preferably, the organic salt includes any one or a combination of at least two of the chloride salt of the amine, the bromide salt of the amine, or the iodide salt of the amine, such as, but not limited to, the chloride salt of the amine and the bromide salt of the amine, the bromide salt of the amine and the iodide salt of the amine, or the chloride salt of the amine and the iodide salt of the amine, and the like, and other combinations not listed within the above-mentioned combinations are also applicable.

Preferably, the perovskite device comprises any one of a solar cell, an LED or a field effect transistor comprising a perovskite material.

Preferably, the amine in step (1) includes any one of methylamine, ethylamine, propylamine or ethanolamine or a combination of at least two thereof, such as a combination of methylamine and ethylamine, a combination of methylamine and propylamine or a combination of propylamine and ethanolamine, and the like, but is not limited to the listed combinations, and other combinations not listed in the above-mentioned combination range are also applicable.

Preferably, the alcohol in step (1) includes any one of methanol, ethanol, n-propanol, isopropanol or tert-butanol or a combination of at least two of them, such as a combination of methanol and ethanol, a combination of methanol and n-propanol or a combination of isopropanol and tert-butanol, etc., but is not limited to the listed combinations, and other combinations not listed in the above-mentioned combination ranges are also applicable.

Preferably, the alcohol solution of the amine in step (1) has a mass fraction of 20-40%, for example 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38% or 40%, etc., but is not limited to the recited values, and other values not recited within the above-mentioned ranges of values are also applicable.

The selection of the specific solvent and the mass fraction can completely separate the functional material from the conductive base material in the perovskite device, and fully recover the conductive base material; the solvent has low toxicity and small influence on human bodies and environment; meanwhile, the boiling point of the solvent is lower than 100 ℃, the solvent is convenient to recover and can be recycled, and the pollution to the environment is reduced.

Preferably, the heating temperature in step (1) is 20 to 100 ℃, for example 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.

The alcohol solution of amine can be fully evaporated by the specific parameters, and can be recycled, so that the environmental pollution is avoided.

Preferably, the solvent in step (2) includes any one or a combination of at least two of dichloromethane, chloroform, carbon tetrachloride, toluene, n-hexane or cyclohexane, for example, a combination of dichloromethane and chloroform, a combination of chloroform and carbon tetrachloride or a combination of toluene and n-hexane, etc., but is not limited to the listed combinations, and other combinations not listed in the above combination range are also applicable.

Preferably, the heating temperature in step (2) is 20 to 100 ℃, for example 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.

The solvent can be fully evaporated by the specific parameters, the solvent can be recycled, the environmental pollution is avoided, the boiling point of the solvent is lower than 100 ℃, the solvent is convenient to recover and can be recycled, and the environmental pollution is reduced.

Preferably, the alcohol in step (3) includes any one of methanol, ethanol, n-propanol, isopropanol or tert-butanol or a combination of at least two of methanol and ethanol, methanol and n-propanol, isopropanol and tert-butanol, and the like, but is not limited to the listed combinations, and other combinations not listed in the above-mentioned combination ranges are also applicable.

The specific alcohol can fully separate the metal halide from the organic salt, fully recover the organic salt and the metal halide, has a boiling point lower than 100 ℃, is convenient to recover, can be recycled, and reduces the environmental pollution.

Preferably, the heating temperature in step (3) is 20 to 100 ℃, for example 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.

The specific parameters can ensure that the alcohol is fully evaporated and can be recycled, thereby avoiding the pollution to the environment.

Preferably, the step (3) further comprises a step (4) after the organic salt is obtained and recovered: crystallizing the halogenated metal obtained in the step (3) as a precursor, and recovering the halogenated metal to obtain the perovskite single crystal.

In the crystallization process, the perovskite single crystal grows by taking the halogenated metal as a precursor, impurities can be removed, the halogenated metal is further purified, and the grown perovskite single crystal can be directly used as a raw material to prepare perovskite precursor liquid and used for preparing other perovskite devices, so that the manufacturing cost of the perovskite devices is saved.

Preferably, the temperature course of the crystallization in the step (4) is as follows: the initial temperature is 100 ℃, and then the temperature is reduced to 60 ℃ at the cooling rate of 0.5-2 ℃/h.

The cooling rate may be 0.5 ℃/h, 0.6 ℃/h, 0.7 ℃/h, 0.8 ℃/h, 0.9 ℃/h, 1 ℃/h, 1.1 ℃/h, 1.2 ℃/h, 1.3 ℃/h, 1.4 ℃/h, 1.5 ℃/h, 1.6 ℃/h, 1.7 ℃/h, 1.8 ℃/h, 1.9 ℃/h, or 2 ℃/h, etc., but is not limited to the values listed, and other values not listed within the above ranges are also applicable.

As a preferred embodiment of the present invention, the recovery method comprises the steps of:

(1) treating the perovskite device with an amine alcoholic solution with the mass fraction of 20-40% to obtain a conductive base material and a first treatment solution, recovering the conductive base material, and heating and evaporating the first treatment solution at the temperature of 20-100 ℃ to obtain a perovskite-functional material mixture;

(2) treating the perovskite-functional material mixture obtained in the step (1) with a solvent, centrifuging to obtain a metal-containing product and a second treatment solution, and heating and evaporating the second treatment solution at 20-100 ℃ to obtain and recover a functional material;

(3) dissolving the metal-containing product obtained in the step (2) with alcohol, performing centrifugal separation to obtain halogenated metal and a third treatment solution, heating and evaporating the third treatment solution at the temperature of 20-100 ℃, and obtaining and recovering organic salt;

(4) crystallizing the halogenated metal obtained in the step (3) as a precursor, and recovering the halogenated metal to obtain the perovskite single crystal.

Compared with the prior art, the invention has the following beneficial effects:

the recovery method provided by the invention is safe and environment-friendly, is simple to operate, can recover all functional materials in the perovskite device, has the metal recovery rate of over 99.5 percent, can recycle the solvent, maximally realizes harmless treatment, and simultaneously can directly use the perovskite single crystal prepared from the recovered halogenated metal for manufacturing the perovskite device, thereby saving the manufacturing cost.

Detailed Description

To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

In the following examples, MAPbI₃The perovskite solar cell is derived from CN107565023A, and has a structure of an ITO/nickel oxide/perovskite/PCBM/silver electrode, wherein the area of the ITO conductive glass is 25mm multiplied by 25mm, and six devices with the areas of 3mm multiplied by 3mm are distributed on the ITO conductive glass.

Example 1

The embodiment provides a method for recycling a perovskite device material, which comprises the following steps:

(1) MAPbI is added₃Soaking the perovskite solar cell in an ethanol solution of methylamine with the mass fraction of 33%, filtering after the perovskite layer is completely dissolved, recovering an insoluble electrode, and distilling the obtained first treatment solution at 40 ℃ under reduced pressure to obtain a perovskite-functional material mixture;

(2) soaking the perovskite-functional material mixture obtained in the step (1) in chloroform, then performing centrifugal separation to obtain a lead-containing product and a second treatment solution, and performing reduced pressure distillation on the second treatment solution at 40 ℃ to obtain and recover a functional material;

(3) dissolving the lead-containing product obtained in the step (1) with ethanol, and then performing centrifugal separation to obtain PdI₂Distilling the residual ethanol solution at 40 ℃ under reduced pressure to obtain and recover organic ammonium salt;

(4) the PdI obtained in the step (3) is used₂Dissolving in 100ml 57% hydriodic acid solution, slowly adding 8ml 33% methylamine ethanol solution dropwise, stirring the secondary precursor solution at 110 deg.C for 1h, adding 5ml formic acid, stirring for 10min, slowly cooling to 60 deg.C at 1 deg.C/h, crystallizing to obtain MAPbI₃Perovskite crystals and calculating lead recovery.

Example 2

The embodiment provides a method for recycling a perovskite device material, which comprises the following steps:

(1) MAPbI is added₃Soaking the perovskite solar cell in an ethanol solution of 20% of ethylamine by mass fraction, filtering after the perovskite layer is completely dissolved, recovering an insoluble electrode, and distilling the obtained first treatment solution at 100 ℃ under reduced pressure to obtain a perovskite-functional material mixture;

(2) soaking the perovskite-functional material mixture obtained in the step (1) in dichloromethane, then carrying out centrifugal separation to obtain a lead-containing product and a second treatment solution, and distilling the second treatment solution at 100 ℃ under reduced pressure to obtain and recover a functional material;

(3) dissolving the lead-containing product obtained in the step (1) with ethanol, and then performing centrifugal separation to obtain PdI₂Distilling the residual ethanol solution at 100 ℃ under reduced pressure to obtain and recover organic ammonium salt;

(4) the PdI obtained in the step (3) is used₂Dissolving in 100ml 57% hydriodic acid solution, slowly adding 8ml 33% methylamine ethanol solution dropwise, stirring the secondary precursor solution at 110 deg.C for 1h, adding 5ml formic acid, stirring for 10min, slowly cooling to 60 deg.C at 0.5 deg.C/h for crystallization to obtain MAPbI₃Perovskite crystals and calculating lead recovery.

Example 3

The embodiment provides a method for recycling a perovskite device material, which comprises the following steps:

(1) MAPbI is added₃Soaking the perovskite solar cell in an n-propanol solution of propylamine with the mass fraction of 40%, filtering after the perovskite layer is completely dissolved, recovering an insoluble electrode, and distilling the obtained first treatment solution at 20 ℃ under reduced pressure to obtain a perovskite-functional material mixture;

(2) soaking the perovskite-functional material mixture obtained in the step (1) in toluene, then carrying out centrifugal separation to obtain a lead-containing product and a second treatment solution, and carrying out reduced pressure distillation on the second treatment solution at the temperature of 20 ℃ to obtain and recover a functional material;

(3) dissolving the lead-containing product obtained in the step (1) by using n-propanol, and then centrifugally separating to obtain PdI₂Distilling the residual n-propanol solution at 20 deg.C under reduced pressure to obtainObtaining and recovering organic ammonium salt;

(4) the PdI obtained in the step (3) is used₂Dissolving in 100ml 57% hydriodic acid solution, slowly adding 8ml 33% methylamine ethanol solution dropwise, stirring the secondary precursor solution at 110 deg.C for 1h, adding 5ml formic acid, stirring for 10min, slowly cooling to 60 deg.C at 2 deg.C/h rate, crystallizing to obtain MAPbI₃Perovskite crystals and calculating lead recovery.

Example 4

The embodiment provides a method for recycling a perovskite device material, which comprises the following steps:

(1) MAPbI is added₃Soaking the perovskite solar cell in a methanol-ethanol mixed solution with the mass fraction of methylamine being 30% and the mass fraction of ethylamine being 10%, wherein the volume ratio of methanol to ethanol is 1:1, filtering after the perovskite layer is completely dissolved, recovering an insoluble electrode, and distilling the obtained first treatment solution at 40 ℃ under reduced pressure to obtain a perovskite-functional material mixture;

(2) soaking the perovskite-functional material mixture obtained in the step (1) in a dichloromethane-chloroform mixed solution, wherein the volume ratio of dichloromethane to chloroform is 1:1, then performing centrifugal separation to obtain a lead-containing product and a second treatment solution, and distilling the second treatment solution at 40 ℃ under reduced pressure to obtain and recover a functional material;

(3) dissolving the lead-containing product obtained in the step (1) by using a methanol ethanol mixed solution, wherein the volume ratio of methanol to ethanol is 1:1, and then centrifugally separating to obtain PdI₂Distilling the residual methanol-ethanol mixed solution at 40 ℃ under reduced pressure to obtain and recover organic ammonium salt;

(4) the PdI obtained in the step (3) is used₂Dissolving in 100ml 57% hydriodic acid solution, slowly adding 8ml 33% methylamine ethanol solution dropwise, stirring the secondary precursor solution at 110 deg.C for 1h, adding 5ml formic acid, stirring for 10min, slowly cooling to 60 deg.C at 1 deg.C/h rate, crystallizing to obtain MAPbI₃Perovskite crystals and calculating lead recovery.

Example 5

This example provides a process for the recovery of perovskite device material, which is identical to that of example 1 except that in step (1) the ethanolic solution of methylamine is replaced with an equal amount of ethanolic solution of propylamine.

Example 6

This example provides a process for recovering a perovskite device material, which is the same as example 1 except that the ethanol solution of methylamine is replaced with an equal amount of ethanol solution of ethanolamine in step (1).

Example 7

This example provides a process for recovering a perovskite device material, which is the same as example 1 except that in step (1) the ethanol solution of methylamine is replaced with an equal amount of n-propanol solution of methylamine.

Example 8

This example provides a process for recovering a perovskite device material, which is the same as example 1 except that in step (1) the ethanol solution of methylamine is replaced with an equal amount of tert-butanol solution of methylamine.

Example 9

This example provides a method of recovering a perovskite device material, consistent with example 1 except that chloroform was replaced with an equal amount of dichloromethane in step (2).

Example 10

This example provides a method of recovering a perovskite device material, consistent with example 1 except that chloroform was replaced with an equal amount of toluene in step (2).

Example 11

This example provides a method for recovering a perovskite device material, which is the same as example 1 except that chloroform was replaced with an equal amount of n-hexane in step (2).

Example 12

This example provides a process for recovering perovskite device material, consistent with example 1 except that in step (3) the same amount of methanol was substituted for ethanol.

Example 13

This example provides a process for recovering a perovskite device material, which was identical to that of example 1 except that in step (3) ethanol was replaced with an equal amount of n-propanol.

Example 14

This example provides a process for recovering a perovskite device material, consistent with example 1 except that in step (3) the ethanol is replaced with an equal amount of isopropanol.

And (4) counting the recovery rate:

the lead recovery rate in each example was calculated by the formula of lead recovery rate (PdI obtained in step (3))₂Mass of medium lead/MAPbI₃Lead mass in perovskite solar cells) x 100%.

The results are as follows:

group of	Lead recovery (%)	Group of	Lead recovery (%)
				Example 1	99.9	Example 8	99.8
Example 2	99.9	Example 9	99.6
				Example 3	99.9	Example 10	99.7
Example 4	99.6	Example 11	99.9
				Example 5	99.8	Example 12	99.6
Example 6	99.8	Example 13	99.8
				Example 7	99.7	Example 14	99.5

The data show that the recovery method of the perovskite device material provided by the invention can achieve an excellent recovery effect on metals in the perovskite device.

The applicant states that the present invention is illustrated by the above examples of the recovery method of the perovskite device material of the present invention, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.