CN115000239B - Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass - Google Patents
Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass Download PDFInfo
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- CN115000239B CN115000239B CN202210509989.3A CN202210509989A CN115000239B CN 115000239 B CN115000239 B CN 115000239B CN 202210509989 A CN202210509989 A CN 202210509989A CN 115000239 B CN115000239 B CN 115000239B
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- 229910001369 Brass Inorganic materials 0.000 title claims abstract description 50
- 239000010951 brass Substances 0.000 title claims abstract description 50
- 239000002243 precursor Substances 0.000 title claims abstract description 35
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002386 leaching Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 title abstract description 11
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 239000011701 zinc Substances 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000011135 tin Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 16
- 150000003751 zinc Chemical class 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 75
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910000928 Yellow copper Inorganic materials 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- H01L31/0248—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
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- 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
-
- 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
Abstract
The invention discloses a method for preparing a copper zinc tin sulfur selenium film solar cell precursor solution by a one-step method of acid leaching brass. According to the method, the copper zinc tin sulfur selenium film solar cell precursor solution is directly synthesized from waste brass through acid leaching, an aqueous solution used for common acid leaching is replaced by an organic solvent, and the leached solution can be directly used as the copper zinc tin sulfur selenium precursor solution. The method has the advantages of short flow, simple operation and low cost, and can efficiently utilize the renewable resources to prepare the copper-zinc-tin-sulfur-selenium thin film solar cell.
Description
Technical Field
The invention relates to the field of thin film solar cells, in particular to a method for preparing a copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass.
Background
Copper is the third place behind steel and aluminum in the consumption of all nonferrous metals worldwide. Copper is an important industrial raw material, and economic, technological and social development factors influence the supply and demand of copper. Brass materials, the main component of which is copper-zinc alloy, are widely applied to a plurality of fields of industrial production, daily life and the like, and the amount of waste brass is huge each year. The traditional brass material recovery process mainly comprises the steps of separating copper from zinc materials, separating copper to form copper sulfide precipitate and zinc, and reducing copper and zinc ions into metal simple substances, wherein the recovery process is complex and the recovery cost is high.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems.
The invention aims to provide a method for directly preparing a copper zinc tin sulfur selenium precursor solution from waste brass by a one-step method.
In order to achieve the above purpose, the method for preparing the copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass provided by the invention comprises the following steps:
A. washing
Ultrasonically washing the brass with a cleaning agent, wherein the cleaning agent comprises one or more of ethanol, isopropanol and acetone;
B. leaching out
Adding hydrochloric acid, an oxidant and an organic solvent into the brass cleaned in the step A, stirring at 20-40 ℃, and filtering the stirred substances to obtain filter residues and filtrate; wherein, the solid-liquid ratio is 1:10-20, stirring speed is 200-400rpm;
C. evaporation
Placing the filtrate obtained in the step B on a hot table for stirring, wherein the stirring speed is 200-400rpm, heating to 80-120 ℃, and evaporating the solvent to obtain copper-zinc precursor solution and hydrogen chloride gas;
D. zinc salt and tin salt are added according to the proportion
And C, adding zinc salt, tin salt and a sulfur source into the copper-zinc precursor solution obtained in the step C to obtain a precursor solution for preparing the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the addition amount of the zinc salt, the tin salt and the sulfur source is determined according to the content of copper and zinc in the copper-zinc precursor solution obtained in the step C and the ratio of copper, zinc and tin in the copper-zinc-tin-sulfur-selenium thin film solar cell precursor solution.
Preferably, in the step a, the solid-to-liquid ratio of brass and the cleaning agent is 1:10-30, and the temperature is 20-70 ℃ during washing.
Preferably, the solid-to-liquid ratio in the step a is 1:20, the ultrasonic frequency is 30kHz, and the temperature is 30-40 ℃.
Preferably, in the step B, the oxidizing agent is H 2 O 2 The organic solvent is one or more of N, N-dimethylformamide, ethylene glycol methyl ether and dimethyl sulfoxide.
Preferably, in the step B, the concentration of hydrochloric acid is 36% -38%.
Preferably, in the step B, the solid-to-liquid ratio is 1:12, the stirring speed is 300rpm, and the stirring temperature is 20-30 ℃.
Preferably, in the step C, the evaporated hydrogen chloride gas is recycled into the step B for reuse.
Preferably, in the step D, 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.
Preferably, in the step D, the sulfur source is thiourea.
The basic idea and technical principle of the invention are as follows:
the brass surface may be contaminated with oil stains and other pollutants, and the brass surface can be removed by ultrasonic treatment with a cleaning agent such as ethanol. Brass can not react or dissolve in the cleaning process, no loss is caused, and the cleaning agents such as ethanol and the like after ultrasonic cleaning can be repeatedly used.
Carrying out oxidation acid leaching on the cleaned brass, wherein the copper-zinc reaction formula in the brass is as follows:
Me+2HCl+H 2 O 2 ＝MeCl 2 +2H 2 O
Me＝Cu、Zn
the traditional brass recovery mode is to leach the brass into an aqueous solution and finally evaporate and crystallize the brass to obtain a product, and the configuration of the copper zinc tin sulfur selenium precursor solution requires the use of an organic solvent to dissolve copper salt and zinc salt. Hydrochloric acid with thinner concentration and H 2 O 2 The copper and zinc can not react with the organic solvent, the main components in the brass are copper and zinc, and the chloride salts of the two elements can be dissolved in the organic solvent, so that the organic solvent can be directly used for leaching, and the yellow transparent solution is obtained through complete leaching. Trace insoluble impurities in brass can be removed by filtration.
The leaching solution is acidic, the boiling point of an organic solvent such as N, N-Dimethylformamide (DMF) is 153 ℃ and higher than the boiling point of hydrochloric acid and water, the hydrochloric acid and the water in the solution are volatilized through evaporation, the leaching solution is recycled and enters an acid leaching link again, and after hydrogen chloride and water are completely evaporated, the finally obtained product is a solution of chloride salts of copper and zinc. The aqueous solution of the chloride salts of copper and zinc is blue-green, and is dissolved in an organic solvent to be yellow, and the end point of evaporation is determined by taking the obtained yellow transparent solution as a judgment basis.
The organic solvent has good solubility to the metal salt, and the metal salt can be continuously added into the solution obtained in the last step. And weighing a certain amount of zinc salt, tin salt and sulfur source according to the proportion of the zinc salt, tin salt and sulfur source required by the precursor solution, and dissolving the zinc salt, the tin salt and the sulfur source in the solution obtained in the last step to obtain the precursor solution of the copper zinc tin sulfur selenium thin film solar cell.
Compared with the prior art, the invention has the following beneficial effects:
directly using waste brass as a raw material, adding zinc salt and tin salt according to the proportion of metal elements in the precursor to obtain a copper zinc tin sulfur selenium film solar cell precursor solution, recycling brass waste by a simple and reliable method, and reducing the cost for preparing the copper zinc tin sulfur selenium precursor. The precursor solution is obtained by using an organic solvent one-step method without complex copper-zinc separation, recrystallization and resolubilization processes, and the intermediate product can be recycled, so that the flow is effectively shortened, the energy consumption is reduced, and the production of waste gas, waste water and waste residues is reduced.
Drawings
FIG. 1 is a process flow chart of preparing a precursor solution of a copper zinc tin sulfur selenium thin film solar cell by pickling brass.
Detailed Description
The invention is further elucidated below in connection with the drawings and the detailed description, without thereby restricting the invention to the scope of the examples described.
Example 1
10g of brass is used as a raw material, wherein the mass of copper is 6.4g, and the mass of zinc is 3.6g.
A. Washing
10g of brass was added to 100ml of ethanol and sonicated at a frequency of 30kHz for twenty minutes at 20℃and filtered to remove surface stains.
B. Oxidation acid leaching
The washed brass was poured into 110ml of N, N-dimethylformamide, 10ml of 36% HCl was added thereto, and stirring was started, and 8ml of H was added thereto while stirring 2 O 2 Followed by open stirring at a temperature of 20℃and a speed of 300 rpm. Brass is completely dissolved to generate copper ions and zinc ions. The resulting solution was filtered using an organic filter head to remove insoluble impurities.
C. Evaporation
And B, placing the filtrate obtained in the step B on a hot table at 110 ℃ for stirring and heating, so that water and hydrochloric acid in the solution are evaporated. The hydrochloric acid obtained by evaporation can be recycled into the step B for reuse. The solution changed from green to yellow when the hydrochloric acid and water evaporated completely.
D. Zinc salt and tin salt are added according to the proportion
The solution obtained in step C was an N, N-dimethylformamide solution of copper chloride and zinc chloride, according to Cu/zn=64: 36, calculating to obtain the molar ratio of Cu/Zn of 1.83, adding 3.33g of zinc acetate and 11.07g of stannous chloride into the solution, stirring the solution, completely dissolving the solution to be green, continuously adding 34.89g of thiourea into the solution, and completely dissolving the solution to obtain the yellow copper zinc tin sulfur selenium precursor solution. The molar ratio of Cu/(Zn+Sn) in the solution was 0.75, the molar ratio of Zn/Sn was 1.2, and the molar ratio of (Cu+Zn+Sn)/S was 0.5.
Example 2
10g of brass is used as a raw material, wherein the mass of copper is 6.4g, and the mass of zinc is 3.6g.
A. Washing
10g of brass was added to 300ml of isopropanol and sonicated at a frequency of 30kHz for twenty minutes at 50℃and filtered to remove surface stains.
B. Oxidation acid leaching
The cleaned brass is put into 130ml of mixed organic solvent of N, N-dimethylformamide and 20ml of dimethyl sulfoxide, 12ml of HCl with 37 percent concentration is added, and stirring is started8ml of H was added with stirring 2 O 2 Followed by open stirring at a temperature of 40℃at 400 rpm. Brass is completely dissolved to generate copper ions and zinc ions. The resulting solution was filtered using an organic filter head to remove insoluble impurities.
C. Evaporation
And B, placing the filtrate obtained in the step B on a hot table at 80 ℃ for stirring and heating, so that water and hydrochloric acid in the solution are evaporated. The hydrochloric acid obtained by evaporation can be recycled into the step B for reuse. The solution changed from green to yellow when the hydrochloric acid and water evaporated completely.
D. Zinc salt and tin salt are added according to the proportion
The solution obtained in step C was an N, N-dimethylformamide solution of copper chloride and zinc chloride, according to Cu/zn=64: 36, calculating to obtain the molar ratio of Cu/Zn of 1.83, adding 4.29g of zinc acetate and 12.4g of stannous chloride into the solution, stirring the solution, completely dissolving the solution to be green, continuously adding 37.61g of thiourea into the solution, and completely dissolving the solution to obtain the yellow copper zinc tin sulfur selenium precursor solution. The molar ratio of Cu/(Zn+Sn) in the solution was 0.70, the molar ratio of Zn/Sn was 1.2, and the molar ratio of (Cu+Zn+Sn)/S was 0.5.
Example 3
10g of brass is used as a raw material, wherein the mass of copper is 6.4g, and the mass of zinc is 3.6g.
A. Washing
10g of brass was added to 200ml of ethanol and sonicated at 30kHz for twenty minutes at 30℃and filtered to remove surface stains.
B. Oxidation acid leaching
The washed brass was poured into 130ml of dimethyl sulfoxide, 10ml of 37% HCl was added, stirring was started, and 8ml of H was added while stirring 2 O 2 Followed by open stirring at a temperature of 30℃and a speed of 200 rpm. Brass is completely dissolved to generate copper ions and zinc ions. The resulting solution was filtered using an organic filter head to remove insoluble impurities.
C. Evaporation
And B, placing the filtrate obtained in the step B on a hot table at 120 ℃ for stirring and heating, so that water and hydrochloric acid in the solution are evaporated. The hydrochloric acid obtained by evaporation can be recycled into the step B for reuse. The solution changed from green to yellow when the hydrochloric acid and water evaporated completely.
D. Zinc salt and tin salt are added according to the proportion
The solution obtained in step C was an N, N-dimethylformamide solution of copper chloride and zinc chloride, according to Cu/zn=64: 36, calculating to obtain the molar ratio of Cu/Zn of 1.83, adding 2.95g of zinc acetate and 10.38g of stannous chloride into the solution, stirring the solution, completely dissolving the solution to be green, continuously adding 30.52g of thiourea into the solution, and completely dissolving the solution to obtain the yellow copper zinc tin sulfur selenium precursor solution. The molar ratio of Cu/(Zn+Sn) in the solution was 0.80, the molar ratio of Zn/Sn was 1.3, and the molar ratio of (Cu+Zn+Sn)/S was 0.5.
Example 4
10g of brass is used as a raw material, wherein the mass of copper is 6.4g, and the mass of zinc is 3.6g.
A. Washing
10g of brass was added to 200ml of a mixture of ethanol and isopropanol, sonicated at a frequency of 30kHz for twenty minutes at 20℃and filtered to remove surface stains.
B. Oxidation acid leaching
The washed brass was poured into 170ml of ethylene glycol methyl ether, 15ml of 38% HCl was added, stirring was started, and 8ml of H was added while stirring 2 O 2 Followed by open stirring at 400rpm at a temperature of 30 ℃. Brass is completely dissolved to generate copper ions and zinc ions. The resulting solution was filtered using an organic filter head to remove insoluble impurities.
C. Evaporation
And B, placing the filtrate obtained in the step B on a hot table at 100 ℃ for stirring and heating, so that water and hydrochloric acid in the solution are evaporated. The hydrochloric acid obtained by evaporation can be recycled into the step B for reuse. The solution changed from green to yellow when the hydrochloric acid and water evaporated completely.
D. Zinc salt and tin salt are added according to the proportion
The solution obtained in step C was an N, N-dimethylformamide solution of copper chloride and zinc chloride, according to Cu/zn=64: 36, calculating to obtain the molar ratio of Cu/Zn of 1.83, adding 3.09g of zinc acetate and 13.64g of stannous chloride into the solution, stirring the solution, completely dissolving the solution to be green, continuously adding 37.61g of thiourea into the solution, and completely dissolving the solution to obtain the yellow copper zinc tin sulfur selenium precursor solution. The molar ratio of Cu/(Zn+Sn) in the solution was 0.70, the molar ratio of Zn/Sn was 1.0, and the molar ratio of (Cu+Zn+Sn)/S was 0.5.
Claims (5)
1. The method for preparing the copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass is characterized by comprising the following steps of:
A. washing
Ultrasonically washing the brass with a cleaning agent, wherein the cleaning agent comprises one or more of ethanol, isopropanol and acetone;
B. leaching out
Adding hydrochloric acid, an oxidant and an organic solvent into the brass cleaned in the step A, stirring at 20-40 ℃, and filtering the stirred substances to obtain filter residues and filtrate; wherein, the solid-liquid ratio is 1:10-20, stirring speed of 200-400rpm, hydrochloric acid concentration of 36-38%, and oxidant of H 2 O 2 The organic solvent is one or more of N, N-dimethylformamide, ethylene glycol methyl ether and dimethyl sulfoxide;
C. evaporation
B, placing the filtrate obtained in the step B on a hot table, stirring at 200-400rpm, heating to 80-120 ℃, and completely evaporating hydrogen chloride and water to obtain copper-zinc precursor solution and hydrogen chloride gas, wherein the end point of evaporation is determined by taking the obtained yellow transparent solution as a judgment basis; the hydrogen chloride gas obtained by evaporation is circulated and enters the step B for reuse;
D. zinc salt and tin salt are added according to the proportion
And C, adding zinc salt, tin salt and a sulfur source into the copper-zinc precursor solution obtained in the step C to obtain a precursor solution for preparing the copper-zinc-tin-sulfur-selenium thin film solar cell, wherein the molar ratio of Cu/(Zn+Sn) is 0.7-1.0, the molar ratio of Zn/Sn is 1.0-1.3, the molar ratio of (Cu+Zn+Sn)/S is 0.5, and the addition amount of the zinc salt, the tin salt and the sulfur source is determined according to the content of copper and zinc in the copper-zinc precursor solution obtained in the step C and the ratio of copper, zinc and tin in the copper-zinc-tin-sulfur-selenium thin film solar cell precursor solution.
2. The method for preparing the copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass according to claim 1, wherein in the step A, the solid-to-liquid ratio of the brass to the cleaning agent is 1:10-30, and the temperature is 20-70 ℃ during washing.
3. The method for preparing the copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass according to claim 2, wherein the solid-to-liquid ratio in the step A is 1:20, the ultrasonic frequency is 30kHz, and the temperature is 30-40 ℃.
4. The method for preparing the copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass according to claim 1, wherein in the step B, the solid-to-liquid ratio is 1:12, the stirring speed is 300rpm, and the stirring temperature is 20-30 ℃.
5. The method for preparing a copper zinc tin sulfur selenium thin film solar cell precursor solution by pickling brass according to claim 1, wherein in the step D, a sulfur source is thiourea.
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