CN113410338B - Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass - Google Patents

Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass Download PDF

Info

Publication number
CN113410338B
CN113410338B CN202110678331.0A CN202110678331A CN113410338B CN 113410338 B CN113410338 B CN 113410338B CN 202110678331 A CN202110678331 A CN 202110678331A CN 113410338 B CN113410338 B CN 113410338B
Authority
CN
China
Prior art keywords
zinc
copper
tin
sulfur
solar cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110678331.0A
Other languages
Chinese (zh)
Other versions
CN113410338A (en
Inventor
刘芳洋
陈望献
潘逸宁
赵祥云
张宗良
蒋良兴
贾明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202110678331.0A priority Critical patent/CN113410338B/en
Publication of CN113410338A publication Critical patent/CN113410338A/en
Application granted granted Critical
Publication of CN113410338B publication Critical patent/CN113410338B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention provides a method for preparing a precursor of a copper-zinc-tin-sulfur-selenium film solar cell by utilizing waste brass, which comprises the steps of washing, alkaline leaching by oxidation, ammonia evaporation, acid dissolution and crystallization sequentially to prepare a copper-zinc alloy in the brass into metal salt required by the precursor of the copper-zinc-tin-sulfur-selenium film solar cell, remove most impurity elements except copper and zinc, determine the addition amounts of copper salt (or zinc salt), tin salt and a sulfur source according to the obtained content of copper and zinc and the ratio of copper, zinc and tin elements in the copper-zinc-tin-sulfur-selenium material, and add corresponding organic solvent to obtain the precursor solution of the copper-zinc-tin-sulfur-selenium film solar cell. According to the invention, the precursor solution of the copper-zinc-tin-sulfur-selenium solar cell is directly synthesized from the waste metal by a one-step method, a copper-zinc separation step is not needed, and trace impurity residues have no obvious influence on the cell efficiency, so that the consumption of a large amount of acid and alkali liquor and a complex process in the traditional recovery are avoided, and the short-process resource recycling is completed.

Description

Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass
Technical Field
The invention relates to the field of thin film solar cells, in particular to a method for preparing a precursor of a copper-zinc-tin-sulfur-selenium thin film solar cell by utilizing waste brass.
Background
The brass material mainly comprises copper-zinc alloy, is widely applied to various fields such as industrial production, daily life and the like, and has huge amount of waste brass every year. The traditional brass material recovery process mainly comprises the separation of copper and zinc materials, copper is usually firstly formed into copper sulfide precipitate and is separated from zinc, copper and zinc ions are reduced into metal simple substances, the recovery process is complex, and the recovery cost is high.
If copper and zinc elements do not need to be sorted in the brass recovery process, the process flow can be greatly reduced, and the cost is reduced. The precursor of the copper-zinc-tin-sulfur-selenium film solar cell contains two elements of copper and zinc at the same time, so that the requirement of brass recovery without copper-zinc separation can be met. The copper zinc tin sulfur selenium film solar cell is a second generation solar cell and has the following characteristics: flexibility, light weight, low cost and no toxicity. Due to the characteristics, the copper-zinc-tin-sulfur-selenium thin film solar cell has a good development prospect. The copper zinc tin sulfur selenium thin film solar cell mainly comprises a back electrode layer, a light absorption layer (namely a copper zinc tin sulfur selenium material layer), a buffer layer, a window layer and a top electrode layer, wherein the most critical for determining the efficiency of the cell is the copper zinc tin sulfur selenium light absorption layer. The technical route for preparing the copper-zinc-tin-sulfur-selenium thin film solar cell by dissolving three metal salts of copper, zinc and tin and a sulfur source in an organic solvent and coating the solution on the surface of a back electrode layer is verified, so that the copper-zinc-tin-sulfur-selenium thin film solar cell has a wide prospect. At present, the copper zinc tin sulfur selenium precursor material is obtained by taking copper salt, zinc salt, tin salt and organic sulfur source as raw materials for production, and the controllable range of the raw material cost is small.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems.
The invention aims to provide a method for directly synthesizing a copper-zinc-tin-sulfur-selenium precursor from waste brass by a one-step method.
In order to achieve the purpose, the invention provides a method for preparing a copper-zinc-tin-sulfur-selenium film solar cell precursor by using waste brass, which comprises the following steps:
A. washing machine
Stirring and washing the waste brass by using a cleaning agent under the conditions of a liquid-solid ratio of 4-10:1 and a temperature of 25-70 ℃, wherein the cleaning agent comprises one or more of ethanol, isopropanol and acetone;
B. alkaline oxidation leaching
Adding a pH stabilizer, an oxidant and ammonia water into the substance cleaned in the step A, heating to 30-70 ℃, and stirring, wherein the liquid-solid ratio is 5-8:1, the pH is adjusted to 10-11, and the stirring speed is 200-400 rpm; filtering the stirred substance to obtain filter residue and filtrate;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 60-80 ℃, and evaporating the solvent, wherein the obtained ammonia gas can be recycled in the step B for reuse;
D. acid soluble
C, adding an acid-containing aqueous solution into the substance obtained in the step C, and filtering to obtain filter residue and filtrate;
E. evaporation of
D, placing the filtrate in the step D into an open container, heating to 80-100 ℃, completely evaporating the solvent or placing the heated solution into an environment of 0-10 ℃, and quickly crystallizing and separating out through the change of solubility along with the temperature;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E into an organic solvent, and adding copper salt, zinc salt, tin salt and a sulfur source into the organic solvent to obtain the required precursor solution of the copper-zinc-tin-sulfur-selenium film solar cell, wherein the adding amounts of the copper salt, the zinc salt, the tin salt and the sulfur source are determined according to the content of copper and zinc in the substance obtained in the step E and the ratio of copper, zinc and tin in the copper-zinc-tin-sulfur-selenium precursor material.
Preferably, the liquid-solid ratio in the step A is 5:1, and the temperature is 50-60 ℃.
Preferably, in the step B, the pH stabilizer is (NH)4)2CO3Or NH4Cl with the actual dosage being 1.2-2.0 times of the theoretical dosage and the oxidant being H2O2The liquid-solid ratio is 7:1, the heating temperature is 50-70 ℃, the pH value is 10, and the stirring speed is 300 rpm.
Preferably, in step C, the filtrate is heated to 80 ℃.
Preferably, in the step D, the acid is an aqueous solution of hydrochloric acid or acetic acid.
Preferably, in the step E, the temperature for heating and precipitating is 80 ℃, and the temperature for cooling and precipitating is 0 ℃.
Preferably, in the step F, the molar ratio of Cu/(Zn + Sn) in the organic solution is 0.7-1.0, the molar ratio of Zn/Sn is 1.0-1.3, and the molar ratio of (Cu + Zn + Sn)/S is 0.5.
The basic idea and technical principle of the invention are as follows:
the waste brass may be contaminated with organic contaminants such as sludge during the recovery process and may be removed in an ethanol/isopropanol washing process. During the washing process, the brass is insoluble in water without loss, and the washed ethanol/isopropanol can be reused in the washing step.
And then, carrying out oxidation alkaline leaching on the material, wherein the reaction formula of copper and zinc in the brass is as follows:
Me+1/2O2+2NH4OH+2NH4Cl＝[Me(NH3)4]Cl2+3H2O
Me+1/2O2+2NH4OH+(NH4)2CO3＝[Me(NH3)4]CO3+3H2O
Me＝Cu、Zn
the impurities in the waste brass are mainly iron, manganese and aluminum, and in the oxidation alkaline leaching reaction, the iron reacts to generate Fe (OH)3While the manganese will react to form alpha-MnO due to precipitation2Precipitation, the aluminum will react to form Al2O3And the brass is insoluble in ammonia water and ammonium salt solution, so that impurities in the waste brass can be removed. The brass may have traces of insoluble impurities removed by filtration. And determining the end point of the oxidation alkaline leaching reaction by taking the obtained blue transparent solution as a judgment basis.
And (3) the leachate is alkaline, and in order to reduce the consumption of acid in the acid dissolving step and recover ammonia gas for recycling, the leachate is placed in a rotary evaporator for ammonia evaporation treatment. The ammonia gas can be separated from the aqueous solution in the evaporation process and enters the ammonia oxidation leaching link again, so that the recycling of the raw materials is realized, and the pH value can be effectively reduced by ammonia evaporation. The rotary evaporation can effectively reduce the vapor pressure of the solution, so that the solute of the solvent can be quickly separated, the energy consumption is reduced, and meanwhile, the negative pressure environment of the rotary evaporation is convenient for collecting ammonia gas.
Adding excess acid to the ammonia still product if a pH stabilizer is used (NH)4)2CO3The acid dissolution step includes the following two requirements: firstly, providing anions needed by precursor salt, and secondly, reacting CO3 2-The acid solution can be hydrochloric acid or acetic acid aqueous solution. Acetic acid is a weak acid and is partially ionized in water, so the concentration of the aqueous acetic acid solution should not exceed 2 mol/L. If a pH stabilizer is used NH4And Cl, the original anions are not required to be removed in the acid dissolution step, but the acid dissolution can only be performed by using an aqueous solution of hydrochloric acid, so that the influence of the disturbance of the anions on the quality of the precursor is avoided. Filtering the solution after acid dissolution.
Heating the filtrate to 80-100 deg.C in an open container, and dissolving HCl and CH in solvent with increasing temperature3COOH (determined by the kind of acid used in acid dissolution) volatilizes and escapes, and the solvent gradually evaporates, and the final product is chloride or acetate of copper and zinc. Alternatively, when the solution starts to precipitate, the solution may be placed in an environment of 0 to 10 ℃ to rapidly precipitate by utilizing the temperature-dependent change of the solution degree, the precipitate may be used in the next step by filtration, and the remaining solution may be used again in the acid-dissolving step.
And weighing the obtained copper salt, zinc salt and tin salt and sulfur source required by the precursor according to a ratio, and dissolving in an organic solvent to obtain the precursor solution of the copper-zinc-tin-sulfur-selenium film solar cell.
Compared with the prior art for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell, the preparation method has the following beneficial effects:
(1) directly using waste brass as a raw material, and providing the addition of copper salt (or zinc salt) and tin salt in the final precursor according to the proportion of copper and zinc components in the waste brass to obtain the precursor material of the copper-zinc-tin-sulfur-selenium solar cell. The method has the advantages of short flow, low pollution, no need of complex copper-zinc separation, recyclable intermediate product, effective reduction of waste gas, waste water and waste residue, and cost reduction.
(2) The invention directly synthesizes the precursor of copper zinc tin sulfur selenium by a one-step method. The optimal process flow is directly selected according to the anions of the required copper salt and zinc salt, the copper and the zinc are separated without introducing an additional flow, the use amount of chemicals is reduced, and the generation amount of waste gas and waste water is reduced.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a precursor of a copper-zinc-tin-sulfur-selenium film solar cell by using waste brass.
Detailed Description
The following examples are intended to illustrate the invention without further limiting its scope.
The following examples were carried out using the process flow diagram shown in FIG. 1.
Example 1
100g of waste and old recycled brass is taken as a raw material, wherein the mass of copper is about 64.0g, and the mass of zinc is about 35.8 g.
A. Washing machine
Adding 100g of waste and old recovered brass raw materials into 500g of mixed solution of ethanol, isopropanol and acetone at 60 ℃, sufficiently stirring and washing, filtering and removing organic pollutants;
B. alkaline oxidation leaching
180g (NH)4)2CO31200g of distilled water are added and the solution is heated to 50 ℃ until (NH)4)2CO3After complete dissolution, the washed material from step A was added followed by 600g of concentrated ammonia and then 160mL of H2O2And (3) maintaining the solution in an aerobic environment, maintaining the temperature of the solution at 50 ℃, and stirring at the rotating speed of 300rpm, so that the copper-zinc alloy in the brass is oxidized and dissolved into copper ammine complex ions and zinc ammine complex ions. Filtering the obtained solution, and filtering insoluble impurities such as trace iron, manganese, aluminum and the like;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 80 ℃, completely evaporating the solvent, wherein the obtained ammonia gas can circularly enter the step B for reuse;
D. acid soluble
Adding 1.75mol/L acetic acid solution into the substance obtained in the step C until the substance obtained in the step C is completely dissolved;
E. crystallization of
Putting the filtrate obtained in the step D into an open container, heating to 80 ℃, and completely evaporating the solvent;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E, 33.6g of zinc acetate dihydrate, 110.7g of stannous chloride and 348.9g of thiourea into 707mL of glycol methyl ether solvent to obtain a precursor solution of the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn + Sn) in the copper-zinc-tin-sulfur-selenium precursor material is 0.75, the molar ratio of Zn/Sn is 1.2, and the molar ratio of Cu + Zn + Sn)/S is 0.5.
Example 2
100g of waste and old recycled brass is taken as a raw material, wherein the mass of copper is about 64.0g, and the mass of zinc is about 35.8 g.
A. Washing machine
Adding 100g of waste and old recovered brass raw materials into 500g of mixed solution of ethanol, isopropanol and acetone at 60 ℃, sufficiently stirring and washing, filtering and removing organic pollutants;
B. alkaline oxidation leaching
100gNH4Cl 640g of distilled water was added and the solution was heated to 50 ℃ for NH4After Cl was completely dissolved, the washed material of step A was added, followed by 600g of concentrated ammonia and then 160mL of H2O2And (3) maintaining the solution in an aerobic environment, maintaining the temperature of the solution at 50 ℃, and stirring at the rotating speed of 300rpm, so that the copper-zinc alloy in the brass is oxidized and dissolved into copper ammine complex ions and zinc ammine complex ions. Filtering the obtained solution, and filtering insoluble impurities such as trace iron, manganese, aluminum and the like;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 80 ℃, completely evaporating the solvent, wherein the obtained ammonia gas can circularly enter the step B for reuse;
D. acid soluble
Adding concentrated hydrochloric acid to the substance obtained in step C until the substance obtained in step C is completely dissolved;
E. crystallization of
Putting the filtrate obtained in the step D into an open container, heating to 80 ℃, and completely evaporating the solvent;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E, 33.6g of zinc acetate dihydrate, 110.7g of stannous chloride and 348.9g of thiourea into 707mL of glycol methyl ether solvent to obtain a precursor solution of the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn + Sn) in the copper-zinc-tin-sulfur-selenium precursor material is 0.75, the molar ratio of Zn/Sn is 1.2, and the molar ratio of Cu + Zn + Sn)/S is 0.5.
Example 3
100g of waste and old recycled brass is taken as a raw material, wherein the mass of copper is about 64.0g, and the mass of zinc is about 35.8 g.
A. Washing machine
Adding 100g of waste and old recovered brass raw materials into 500g of mixed solution of ethanol, isopropanol and acetone at 60 ℃, sufficiently stirring and washing, filtering and removing organic pollutants;
B. alkaline oxidation leaching
180g (NH)4)2CO31200g of distilled water are added and the solution is heated to 50 ℃ until (NH)4)2CO3After complete dissolution, the washed material from step A was added followed by 600g of concentrated ammonia and then 160mL of H2O2And (3) maintaining the solution in an aerobic environment, maintaining the temperature of the solution at 50 ℃, and stirring at the rotating speed of 300rpm, so that the copper-zinc alloy in the brass is oxidized and dissolved into copper ammine complex ions and zinc ammine complex ions. Filtering the obtained solution, and filtering insoluble impurities such as trace iron, manganese, aluminum and the like;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 60 ℃, completely evaporating the solvent, wherein the obtained ammonia gas can circularly enter the step B for reuse;
D. acid soluble
Adding 1.75mol/L acetic acid solution into the substance obtained in the step C until the substance obtained in the step C is completely dissolved;
E. crystallization of
Putting the filtrate obtained in the step D into an open container, heating to 80 ℃, and completely evaporating the solvent;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E, 33.6g of zinc acetate dihydrate, 110.7g of stannous chloride and 348.9g of thiourea into 707mL of glycol methyl ether solvent to obtain a precursor solution of the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn + Sn) in the copper-zinc-tin-sulfur-selenium precursor material is 0.75, the molar ratio of Zn/Sn is 1.2, and the molar ratio of Cu + Zn + Sn)/S is 0.5.
Example 4
100g of waste and old recycled brass is taken as a raw material, wherein the mass of copper is about 64.0g, and the mass of zinc is about 35.8 g.
A. Washing machine
Adding 100g of waste and old recovered brass raw materials into 500g of mixed solution of ethanol, isopropanol and acetone at 60 ℃, sufficiently stirring and washing, filtering and removing organic pollutants;
B. alkaline oxidation leaching
180g (NH)4)2CO31200g of distilled water are added and the solution is heated to 50 ℃ until (NH)4)2CO3After complete dissolution, the washed material from step A was added followed by 600g of concentrated ammonia and then 160mL of H2O2And (3) maintaining the solution in an aerobic environment, maintaining the temperature of the solution at 50 ℃, and stirring at the rotating speed of 300rpm, so that the copper-zinc alloy in the brass is oxidized and dissolved into copper ammine complex ions and zinc ammine complex ions. Filtering the obtained solution, and filtering insoluble impurities such as trace iron, manganese, aluminum and the like;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 80 ℃, completely evaporating the solvent, wherein the obtained ammonia gas can circularly enter the step B for reuse;
D. acid soluble
Adding 1.75mol/L acetic acid solution into the substance obtained in the step C until the substance obtained in the step C is completely dissolved;
E. crystallization of
Putting the filtrate obtained in the step D into an open container, heating to 100 ℃, and completely evaporating the solvent;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E, 33.6g of zinc acetate dihydrate, 110.7g of stannous chloride and 348.9g of thiourea into 707mL of glycol methyl ether solvent to obtain a precursor solution of the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn + Sn) in the copper-zinc-tin-sulfur-selenium precursor material is 0.75, the molar ratio of Zn/Sn is 1.2, and the molar ratio of Cu + Zn + Sn)/S is 0.5.
Example 5
100g of waste and old recycled brass is taken as a raw material, wherein the mass of copper is about 64.0g, and the mass of zinc is about 35.8 g.
A. Washing machine
Adding 100g of waste and old recovered brass raw materials into 500g of mixed solution of ethanol, isopropanol and acetone at 60 ℃, sufficiently stirring and washing, filtering and removing organic pollutants;
B. alkaline oxidation leaching
180g (NH)4)2CO31200g of distilled water are added and the solution is heated to 50 ℃ until (NH)4)2CO3After complete dissolution, the washed material from step A was added followed by 600g of concentrated ammonia and then 160mL of H2O2And (3) maintaining the solution in an aerobic environment, maintaining the temperature of the solution at 50 ℃, and stirring at the rotating speed of 300rpm, so that the copper-zinc alloy in the brass is oxidized and dissolved into copper ammine complex ions and zinc ammine complex ions. Filtering the obtained solution, and filtering insoluble impurities such as trace iron, manganese, aluminum and the like;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 80 ℃, completely evaporating the solvent, wherein the obtained ammonia gas can circularly enter the step B for reuse;
D. acid soluble
Adding 1.75mol/L acetic acid solution into the substance obtained in the step C until the substance obtained in the step C is completely dissolved;
E. crystallization of
D, placing the filtrate obtained in the step D in an open container, heating to 80 ℃, placing the heated solution in an environment of 0 ℃, rapidly precipitating by utilizing the change of solution temperature along with temperature, filtering to use the precipitate in the next step, and using the rest solution in the acid dissolving step again;
F. copper salt (or zinc salt), tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E, 24.6g of zinc acetate dihydrate, 113.7g of stannous chloride and 345.0g of thiourea into 707mL of glycol methyl ether solvent to obtain a precursor solution of the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn + Sn) in the copper-zinc-tin-sulfur-selenium precursor material is 0.80, the molar ratio of Zn/Sn is 1.1, and the molar ratio of Cu + Zn + Sn)/S is 0.5.

Claims (7)

1. A method for preparing a precursor of a copper-zinc-tin-sulfur-selenium film solar cell by using waste brass is characterized by comprising the following steps:
A. washing machine
Stirring and washing the waste brass by using a cleaning agent under the conditions of a liquid-solid ratio of 4-10:1 and a temperature of 25-70 ℃, wherein the cleaning agent comprises one or more of ethanol, isopropanol and acetone;
B. alkaline oxidation leaching
Adding a pH stabilizer, an oxidant and ammonia water into the substance cleaned in the step A, heating to 30-70 ℃, and stirring, wherein the liquid-solid ratio is 5-8:1, the pH is adjusted to 10-11, and the stirring speed is 200-400 rpm; filtering the stirred substance to obtain filter residue and filtrate;
C. ammonia distillation
Putting the filtrate obtained in the step B into a rotary evaporator, heating to 60-80 ℃, and evaporating the solvent, wherein the obtained ammonia gas can be recycled in the step B for reuse;
D. acid soluble
C, adding an acid-containing aqueous solution into the substance obtained in the step C, and filtering to obtain filter residue and filtrate;
E. evaporation of
D, placing the filtrate in the step D into an open container, heating to 80-100 ℃, completely evaporating the solvent or placing the heated solution into an environment of 0-10 ℃, and quickly crystallizing and separating out through the change of solubility along with the temperature;
F. copper salt, zinc salt, tin salt and sulfur source are added according to the mixture ratio
And E, adding the substance obtained in the step E into an organic solvent, and adding copper salt, zinc salt, tin salt and a sulfur source into the organic solvent to obtain the required precursor solution of the copper-zinc-tin-sulfur-selenium film solar cell, wherein the adding amounts of the copper salt, the zinc salt, the tin salt and the sulfur source are determined according to the content of copper and zinc in the substance obtained in the step E and the ratio of copper, zinc and tin in the copper-zinc-tin-sulfur-selenium precursor material.
2. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium film solar cell by using the waste brass as claimed in claim 1, wherein the liquid-solid ratio in the step A is 5:1, and the temperature is 50-60 ℃.
3. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell by using the waste brass as claimed in claim 1, wherein in the step B, the pH stabilizer is (NH)4)2CO3Or NH4Cl with the actual dosage being 1.2-2.0 times of the theoretical dosage and the oxidant being H2O2The liquid-solid ratio is 7:1, the heating temperature is 50-70 ℃, the pH value is 10, and the stirring speed is 300 rpm.
4. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell by using the waste brass as claimed in claim 1, wherein in the step C, the filtrate is heated to 80 ℃.
5. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell by using the waste brass as claimed in claim 1, wherein in the step D, the acid is an aqueous solution of hydrochloric acid or acetic acid.
6. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell by using the waste brass as claimed in claim 1, wherein in the step E, the temperature for heating and separating out is 80 ℃, and the temperature for cooling and separating out is 0 ℃.
7. The method for preparing the precursor of the copper-zinc-tin-sulfur-selenium thin film solar cell by using the waste brass as claimed in claim 1, wherein in the step F, the molar ratio of Cu/(Zn + Sn) is 0.7-1.0, the molar ratio of Zn/Sn is 1.0-1.3, and the molar ratio of Cu + Zn + Sn)/S is 0.5.
CN202110678331.0A 2021-06-18 2021-06-18 Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass Active CN113410338B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110678331.0A CN113410338B (en) 2021-06-18 2021-06-18 Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110678331.0A CN113410338B (en) 2021-06-18 2021-06-18 Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass

Publications (2)

Publication Number Publication Date
CN113410338A CN113410338A (en) 2021-09-17
CN113410338B true CN113410338B (en) 2022-04-29

Family

ID=77681314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110678331.0A Active CN113410338B (en) 2021-06-18 2021-06-18 Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass

Country Status (1)

Country Link
CN (1) CN113410338B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000239B (en) * 2022-05-11 2024-02-23 中南大学 Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass
CN114899279B (en) * 2022-05-11 2023-11-10 中南大学 Preparation method of modified copper zinc tin sulfur precursor solution and thin film solar cell
CN115491497B (en) * 2022-09-22 2024-03-19 广东佳纳能源科技有限公司 Method for recycling valuable metal elements in iron slag and application of method

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130060708A (en) * 2011-11-30 2013-06-10 (주)유성 Recycling method of photovoltaic waste facility
CN103199148A (en) * 2012-01-09 2013-07-10 深圳市格林美高新技术股份有限公司 Method for recycling gallium, indium and germanium from wasted thin-film solar cells
TWI496896B (en) * 2014-04-28 2015-08-21 Univ Nat Cheng Kung Recovery method of copper - free indium gallium selenium residue by heat treatment
CN105057323A (en) * 2015-07-08 2015-11-18 常德汉能薄膜太阳能科技有限公司 Copper-indium-gallium-selenium flexible thin film solar battery recycling method
FR3022074A1 (en) * 2014-06-05 2015-12-11 Imra Europ Sas PROCESS FOR THE PREPARATION OF THIN FILM OF SULFIDE ABSORBER (S) AND SELENIOR (S) OF COPPER, ZINC AND TIN, RECESSED THIN LAYER AND PHOTOVOLTAIC DEVICE OBTAINED
CN108417922A (en) * 2018-01-16 2018-08-17 华北电力大学 A method of being used to prepare solar cell from recycling lead of abandoned lead acid accumulator
CN109678123A (en) * 2018-11-30 2019-04-26 中国科学院物理研究所 Copper zinc tin sulfur selenium thin-film solar cells and its precursor solution preparation method
CN110684904A (en) * 2019-11-19 2020-01-14 江西省科学院能源研究所 Method for recovering copper and tin in waste tinned copper wire
CN111434614A (en) * 2019-08-21 2020-07-21 杭州纤纳光电科技有限公司 Method for recovering and purifying lead iodide
CN111570463A (en) * 2020-04-03 2020-08-25 中国大唐集团科学技术研究院有限公司火力发电技术研究院 Resource treatment method and device for waste solar cell panel
CN111945002A (en) * 2020-07-06 2020-11-17 广东邦普循环科技有限公司 Method for removing copper from waste lithium batteries by recovery wet process
CN112259719A (en) * 2020-10-22 2021-01-22 昆明理工大学 Comprehensive recovery method of waste photovoltaic module and preparation method of silicon-carbon negative electrode material
CN112853101A (en) * 2020-12-31 2021-05-28 北京首创环境科技有限公司 Electroplating sludge recycling treatment method

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130060708A (en) * 2011-11-30 2013-06-10 (주)유성 Recycling method of photovoltaic waste facility
CN103199148A (en) * 2012-01-09 2013-07-10 深圳市格林美高新技术股份有限公司 Method for recycling gallium, indium and germanium from wasted thin-film solar cells
TWI496896B (en) * 2014-04-28 2015-08-21 Univ Nat Cheng Kung Recovery method of copper - free indium gallium selenium residue by heat treatment
FR3022074A1 (en) * 2014-06-05 2015-12-11 Imra Europ Sas PROCESS FOR THE PREPARATION OF THIN FILM OF SULFIDE ABSORBER (S) AND SELENIOR (S) OF COPPER, ZINC AND TIN, RECESSED THIN LAYER AND PHOTOVOLTAIC DEVICE OBTAINED
CN105057323A (en) * 2015-07-08 2015-11-18 常德汉能薄膜太阳能科技有限公司 Copper-indium-gallium-selenium flexible thin film solar battery recycling method
CN108417922A (en) * 2018-01-16 2018-08-17 华北电力大学 A method of being used to prepare solar cell from recycling lead of abandoned lead acid accumulator
CN109678123A (en) * 2018-11-30 2019-04-26 中国科学院物理研究所 Copper zinc tin sulfur selenium thin-film solar cells and its precursor solution preparation method
CN111434614A (en) * 2019-08-21 2020-07-21 杭州纤纳光电科技有限公司 Method for recovering and purifying lead iodide
CN110684904A (en) * 2019-11-19 2020-01-14 江西省科学院能源研究所 Method for recovering copper and tin in waste tinned copper wire
CN111570463A (en) * 2020-04-03 2020-08-25 中国大唐集团科学技术研究院有限公司火力发电技术研究院 Resource treatment method and device for waste solar cell panel
CN111945002A (en) * 2020-07-06 2020-11-17 广东邦普循环科技有限公司 Method for removing copper from waste lithium batteries by recovery wet process
CN112259719A (en) * 2020-10-22 2021-01-22 昆明理工大学 Comprehensive recovery method of waste photovoltaic module and preparation method of silicon-carbon negative electrode material
CN112853101A (en) * 2020-12-31 2021-05-28 北京首创环境科技有限公司 Electroplating sludge recycling treatment method

Also Published As

Publication number Publication date
CN113410338A (en) 2021-09-17

Similar Documents

Publication Publication Date Title
CN113410338B (en) Method for preparing copper-zinc-tin-sulfur-selenium film solar cell precursor by utilizing waste brass
US10336624B2 (en) Method of producing high-plurality lithium carbonate by controlling particle size, particle size distribution, and particle shape
JP6714226B2 (en) Method for producing nickel sulfate, manganese sulfate, lithium sulfate, cobalt sulfate and tricobalt tetroxide from battery waste
CN106542512B (en) Utilize the high-purity phosphoric acid lithium preparation method of the lithium waste liquid of old and useless battery
JP6770676B2 (en) Lithium recovery method
CN101746822B (en) Method for extracting sodium metavanadate from vanadium extraction leaching solution
CN108862335B (en) Method for preparing lithium carbonate from lithium phosphate
CN103771526B (en) A kind of take industrial manganic sulfate as the method that high purity manganese sulfate prepared by raw material
KR101771596B1 (en) Manufacturing method of lithium salt from waste solution containing lithium
CN107056388A (en) The preparation method of chemical polishing waste phosphoric acid processing method and fertilizer
CN114349079A (en) Recycling treatment method for nickel slag solid waste in nitrogen trifluoride gas electrolysis production
CN113104901B (en) Method for preparing iron oxide yellow from rare earth waste acid leaching slag
CN113336268A (en) Method for producing ammonium paratungstate based on tungstic acid
CN114540643B (en) Method for preparing ammonium metavanadate from vanadium-phosphorus-arsenic-containing slag
CN114988478B (en) Method for preparing battery-grade manganese sulfate by synergistic dissolution crystallization of chelating agent
CN114715943A (en) Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method
CN113354048B (en) Heavy metal precipitator, application and preparation method thereof, and waste acid wastewater treatment method
CN103086440B (en) Method for processing cobalt oxalate waste
CN114988464A (en) Method and device for recycling lead salt from perovskite battery
CN1045956A (en) Produce zinc subcarbonate and active zinc flower with ammonium bicarbonate precipitation method
CN113651344A (en) Method for purifying magnesium chloride by using salt lake brine
CN114702075A (en) Purification preparation method of manganese sulfate
CN103663561A (en) Recycling method of molybdenum in filament-melting waste acid
US4508688A (en) Method of regenerating acetate in a metal removal process
CN115000239B (en) Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant