CN102649543A - Method for producing chalcopyrite-type compound - Google Patents

Abstract

The invention is a method for producing a chalcopyrite-type compound, comprising subjecting a reaction mixture to a reflux reaction in a first solvent, and filtering after the reaction to obtain a crude chalcopyrite-type compound; mixing the crude product, a second solvent, and a post-treatment material to form a treatment mixture; and heating the treatment mixture under reflux conditions to remove impurities from the crude product in a manner that allows for post-treatment of the crude product to produce a product containing M¹、M²And a chalcopyrite-type compound of A, M¹Is selected from Cu, Au, Ag, Na, Li or K, the M²Is selected from In, Ga, Al, Ti, Zn, Cd, Sn,Mg or any combination of the foregoing, and the a is selected from S, Se, Te, or any combination of the foregoing. Thus, the production method of the present invention can reduce the content of impurities in the chalcopyrite-type compound.

Description

Method for producing chalcopyrite-type compound

technical field

The invention relates to a method for producing a chalcopyrite-type compound, in particular to a method for producing a post-treated chalcopyrite-type compound comprising a crude product.

Background technique

Chalcopyrite-type compounds, such as CuInSe ₂ , Cu(In _x Ga _1-x )(S _y S _2-y ) and Cu(In _x Al _1-x )(Se _y S _2-y ), have high optoelectronic Due to the advantages of high efficiency and low cost, it is often used to manufacture semiconductor adsorption layers for solar cells. The content of impurities contained in chalcopyrite-type compounds, such as carbon content, has a significant negative effect on the photoelectric efficiency of chalcopyrite-type compounds, so it is expected that chalcopyrite-type compounds with low impurity content can be produced. compound.

Bin Li et al. in Adv. Mater., 1999, 11, No. 17, 1456-1459 disclosed a solvothermal synthesis method for producing CuInSe ₂ nanomaterials. The method comprises reacting a mixture of CuCl ₂ ·2H ₂ O, InCl ₃ ·4H ₂ O and Se powder in ethylenediamine solvent at 180° C. for 15 hours to form a precipitate. The precipitate is washed with an aqueous solution containing ethanol and water to remove by-products in the precipitate, and then dried to form a chalcopyrite-type compound powder with a chalcopyrite phase structure, but the chalcopyrite-type compound The powder has a higher carbon impurity content.

U.S. Patent No. 7,591,990 discloses a process for producing a chalcopyrite-type compound with a molecular formula of M ³ M ¹ A ₂ , M ¹ can be selected from Al ³⁺ , Ga ³⁺ or In ³⁺ , etc., and M ³ can be selected from Cu ⁺ or Ag ^+, etc., and A can be selected from S, Se or Te. The manufacturing process comprises reacting a compound having the molecular formula M ³ X with a compound having the molecular formula M ² M ¹ A ₂ in a coordinating solvent to form a chalcopyrite-type compound having the molecular formula M ³ M ¹ A ₂ , where X can be Halogen atom, M ² can be Li ⁺ , Na ⁺ , K ⁺ etc. The chalcopyrite-type compounds produced by this process also have a relatively high impurity content.

This shows that above-mentioned existing method for the manufacture of chalcopyrite-type compound obviously still has inconvenience and defect in method and use, and urgently needs to be further improved. In order to solve the above-mentioned problems, the relevant manufacturers have tried their best to find a solution, but no suitable design has been developed for a long time, and the general method has no suitable method to solve the above-mentioned problems. This is obviously related. The problem that the industry is eager to solve. Therefore, how to create a new manufacturing method of chalcopyrite-type compounds is one of the current important research and development topics, and it has also become a goal that the industry needs to improve.

Contents of the invention

The purpose of the present invention is to overcome the defects in the existing chalcopyrite-type compound manufacturing method, and provide a new method for the manufacture of chalcopyrite-type compounds, the technical problem to be solved is to make it possible to reduce the chalcopyrite-type compound The content of impurities in type compounds is very suitable for practical use. The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions. According to a method for producing a chalcopyrite-type compound proposed by the present invention, the method includes allowing the reaction mixture to undergo a reflux reaction in a first solvent; filtering the reacted reaction mixture to obtain a crude product of the chalcopyrite-type compound; The product, the second solvent, and a post-treatment material are mixed to form a treatment mixture, the post-treatment material is selected from S, Se, Te, or any combination thereof; and the treatment mixture is made to allow the crude product to be post-treated The method can be heated under reflux conditions to remove impurities from the crude product to generate chalcopyrite-type compounds containing M ¹ , M ² and A, and M ¹ is selected from Cu, Au, Ag, Na, Li or K, the ^M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or any combination of the foregoing, and the A is selected from S, Se, Te or any of the foregoing combination.

The purpose of the present invention and its technical problems can also be further realized by adopting the following technical measures.

Preferably, the aforementioned method for producing chalcopyrite-type compounds, wherein the first solvent and the second solvent are each independently selected from alkylamine, dimethylformamide, nitrogen-methyltetrahydro Pyrrolidone, Methimidazole, Dimethylsulfoxide, Oleylamine, Glycerin or Ethylene Glycol.

Preferably, in the aforementioned method for producing a chalcopyrite-type compound, the first solvent and the second solvent are each independently selected from ethylenediamine or methylimidazole.

Preferably, the aforementioned method for producing a chalcopyrite-type compound further comprises a cleaning step before forming the treatment mixture, the cleaning step is to wash the crude product by using a cleaning solution, and the cleaning solution includes water, alcohol and acetone .

Preferably, the aforementioned method for producing a chalcopyrite-type compound further includes a step of filtering the post-treated reaction mixture to obtain a treated crude product, and then washing the treated crude product with a cleaning solution. Crude product, the wash solution includes water, alcohol and acetone.

Preferably, the aforementioned method for producing a chalcopyrite-type compound further includes a step of washing the treated crude product with an acid solution.

Preferably, the aforementioned method for producing chalcopyrite-type compounds, wherein the reaction mixture includes at least one first compound and at least one second compound, the first compound includes M ¹ and A ¹ , the second compound includes M ² and A ¹ , the A ¹ is selected from S, Se, Te, Cl ^- , Br ^- , I ^- , OH ^- , NO ₃ ^- , SO ₄ ^2- , CH ₃ COO ^- , acetylacetonate ion or Any combination of S, Se and Te; and when A ¹ of the first compound and the second compound is selected from Cl ^- , Br ^- , I ^- , OH ^- , NO ₃ ^- , SO ₄ ^2- , CH ₃ ^COO- or acetylacetonate ion, the reaction mixture further comprises powder, the powder is selected from S, Se, Te or any combination of the foregoing.

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes Cu ₂ Se and In ₂ Se ₃ .

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes Cu ₂ Se, In ₂ Se ₃ and Ga ₂ Se ₃ .

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes Cu ₂ Se, In ₂ S ₃ and Ga ₂ Se ₃ .

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes Se, InCl ₃ ·4H ₂ O and CuCl.

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes InCl ₃ , Na ₂ Se and CuCl.

Preferably, in the aforementioned method for producing chalcopyrite-type compounds, the reaction mixture includes InCl ₃ , GaCl ₃ , Na ₂ Se and CuCl.

Compared with the prior art, the present invention has obvious advantages and beneficial effects. By means of the above technical solution, the method for producing the chalcopyrite-type compound of the present invention has at least the following advantages and beneficial effects: The production method of the present invention can reduce the content of impurities in the chalcopyrite-type compound.

In summary, the present invention relates to a method for producing a chalcopyrite-type compound, which includes allowing the reaction mixture to undergo a reflux reaction in a first solvent, and filtering after the reaction to obtain a crude product of a chalcopyrite-type compound; combining the crude product, the second solvent, and the work-up material to form a work-up mixture; and heating the work-up mixture under reflux conditions to remove impurities from the crude product in a manner that permits work-up of the crude product, to Generate a chalcopyrite compound containing M ¹ , M ² and A, M ¹ is selected from Cu, Au, Ag, Na, Li or K, and the M ² is selected from In, Ga, Al, Ti, Zn , Cd, Sn, Mg or any combination of the foregoing, and the A is selected from S, Se, Te or any combination of the foregoing. The present invention has significant progress in technology, and has obvious positive effects, and is a novel, progressive and practical new design.

The above description is only an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention, it can be implemented according to the contents of the description, and in order to make the above and other purposes, features and advantages of the present invention more obvious and understandable , the following preferred embodiments are specifically cited below, and are described in detail as follows in conjunction with the accompanying drawings.

Description of drawings

FIG. 1 is an X-ray diffraction diagram illustrating the product (c) obtained in Example 1 without post-treatment.

FIG. 2 is an X-ray diffraction diagram illustrating the post-treated product (d) obtained in Example 1. FIG.

Figure 3 is an X-ray diffraction diagram illustrating the post-treated and washed product (e) obtained in Example 1.

FIG. 4 is an X-ray diffraction diagram illustrating the product (f) obtained in Example 2 without post-treatment.

Figure 5 is an X-ray diffraction diagram illustrating the after-treated product (g) obtained in Example 2;

FIG. 6 is an X-ray diffraction diagram illustrating the post-treated product (h) obtained in Example 2 and washed with an acid solution.

FIG. 7 is an X-ray diffraction diagram illustrating the non-post-treated product (i) obtained in Example 3. FIG.

FIG. 8 is an X-ray diffraction diagram illustrating the post-treated product (j) obtained in Example 3. FIG.

Figure 9 is an X-ray diffraction pattern illustrating the post-treated and washed product (k) with an acid obtained in Example 3.

FIG. 10 is an X-ray diffraction diagram illustrating the non-post-treated product (1) obtained in Example 4.

FIG. 11 is an X-ray diffraction diagram illustrating the post-treated product (m) obtained in Example 4. FIG.

FIG. 12 is an X-ray diffraction diagram illustrating the non-post-treated product (n) obtained in Example 5. FIG.

FIG. 13 is an X-ray diffraction diagram illustrating the post-treated product (o) obtained in Example 5. FIG.

FIG. 14 is an X-ray diffraction diagram illustrating the non-post-treated product (p) obtained in Example 6. FIG.

FIG. 15 is an X-ray diffraction diagram illustrating the post-treated product (q) obtained in Example 6. FIG.

FIG. 16 is an X-ray diffraction diagram illustrating the non-post-treated product (r) obtained in Example 7. FIG.

FIG. 17 is an X-ray diffraction diagram illustrating the post-treated product(s) obtained in Example 7. FIG.

FIG. 18 is an X-ray diffraction diagram illustrating the non-post-treated product (t) obtained in Example 8. FIG.

FIG. 19 is an X-ray diffraction diagram illustrating the post-treated product (u) obtained in Example 8. FIG.

FIG. 20 is an X-ray diffraction diagram illustrating the product (v) produced in Comparative Example 1. FIG.

FIG. 21 is an X-ray diffraction diagram illustrating a product (w) obtained in Comparative Example 2. FIG.

FIG. 22 is an X-ray diffraction diagram illustrating a product (x) obtained in Comparative Example 3. FIG.

Detailed ways

For further elaborating the technical means and effect that the present invention takes to reach the intended invention purpose, below in conjunction with accompanying drawing and preferred embodiment, to its specific implementation, method, Steps, features and effects thereof are described in detail below.

The aforementioned and other technical contents, features and effects of the present invention will be clearly presented in the following detailed description of preferred embodiments with reference to the drawings. Through the description of the specific implementation mode, a more in-depth and specific understanding of the technical means and effects adopted by the present invention to achieve the intended purpose can be obtained. However, the accompanying drawings are only for reference and description, and are not used to explain the present invention. be restricted.

A preferred specific example of the production method of the chalcopyrite-type compound of the present invention includes allowing the reaction mixture to undergo a reflux reaction in a first solvent; filtering the reacted reaction mixture to obtain a crude product of the chalcopyrite-type compound; The product, the second solvent and the post-treatment material are mixed to form a treatment mixture, the post-treatment material is selected from S, Se, Te, or any combination of the foregoing; and the treatment mixture is allowed to undergo a post-treatment of the crude product can be heated under reflux conditions to remove impurities from the crude product in a manner to generate chalcopyrite-type compounds containing M ¹ , M ² and A, M ¹ being selected from Cu, Au, Ag, Na , Li or K, the ^M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or any combination of the foregoing, and the A is selected from S, Se, Te or any of the foregoing a combination.

The reaction mixture comprises at least one first compound and at least one second compound, the first compound includes M ¹ and A ¹ , the second compound includes M ² and A ¹ , the A ¹ is selected from S, Se, Te , Cl ^- , Br ^- , I ^- , OH ^- , NO ₃ ^- , SO ₄ ^2- , CH ₃ COO ^- , acetylacetonate ion or any combination of S, Se and Te.

When the ^A of the first compound and the second compound is not S, Se, Te, or any combination of S, Se and Te, the reaction mixture also includes powder, the powder is selected from S, Se, Te or any combination of the foregoing.

In a preferred embodiment of the present invention, the manufacturing method further includes washing the treated crude product with a cleaning solution before mixing the crude product, the second solvent and the post-treatment powder, and the cleaning solution includes water, alcohol and acetone, followed by drying the treated crude product.

Preferably, in a preferred embodiment of the present invention, the manufacturing method further comprises washing the crude product of the chalcopyrite-type compound with an acid solution after the post-treatment, and then washing the crude product with the washing solution, and dry the crude product.

The first solvent and the second solvent suitable for the present invention can be such as alkylamine, dimethylformamide (DMF), nitrogen-methyltetrahydropyrrolidone (NMP), methylimidazole, dimethyl sulfoxide (DMSO) , oleylamine, glycerin or ethylene glycol, etc. In a preferred embodiment of the present invention, the first solvent and the second solvent are each independently selected from ethylenediamine or methylimidazole.

Suitable examples of acids contained in the acid solution include nitric acid, hydrochloric acid, citric acid, acetic acid, phosphoric acid, sulfuric acid and oxalic acid. Preferably, when the selected acid is a strong acid, the concentration range of the strong acid is 5-10 wt%.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limitations on the implementation of the present invention.

<Example 1 (E1)>

Preparation of In ₂ Se ₃

Add 4000 mL of ethylenediamine into the reaction tank, and then add 302.5 g of Se powder while stirring. After stirring for 5 minutes, slowly add 750.5 g of InCl ₃ ·4H ₂ O while stirring to form a mixture. After stirring the mixture in the reaction tank for 20 minutes, the stirring was continued while heating to the boiling point. The mixture was continuously subjected to reflux reaction for 30 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain crude In ₂ Se ₃ . The crude In ₂ Se ₃ product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed crude In ₂ Se ₃ was dried at 150° C. to obtain yellow powder In ₂ Se ₃ [product (a)]. The composition of the product (a) contains 42.63 at % In and 57.37 at % Se. Elemental analysis of the yellow powder showed 4.81% by weight of carbon impurities.

Preparation of Cu ₂ Se

Add 5500 mL of ethylenediamine into the reaction tank, and then add 231 g of Se powder while stirring. After stirring for 5 minutes, slowly add 580 g of CuCl while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The mixture was continued to reflux for 24 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain Cu ₂ Se crude product. The Cu ₂ Se crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed Cu ₂ Se crude product was dried at a temperature of 150° C. to obtain dark blue powder Cu ₂ Se [product (b)]. The composition of the product (b) contains 63.82 at% Cu and 36.18 at% Se. Elemental analysis of the dark blue powder showed 0.1 wt% carbon impurity therein.

Preparation of ternary compound CuInSe ₂

9000 mL of ethylenediamine was added to the reaction tank, and 600 g of product (a) and 260 g of product (b) were added while stirring to form a mixture. After stirring the mixture for 5 minutes, the stirring was continued and heated to boiling point. The mixture was continuously subjected to reflux reaction for 30 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain a _CuInSe2 crude product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (c)]. The composition of the product (c) contains 25.43 at % Cu, 26.68 at % In and 47.89 at % Se. Elemental analysis of the black powder showed 1.536 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (c)] is shown in FIG. 1 .

Remove impurities of product (c)

6000 mL of ethylenediamine was added into the reaction tank, and 730 g of the product (c) and 44 g of Se powder were added while stirring to obtain a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 40 hours to subject the product (c) to a work-up step. After the work-up step was completed and the mixture was cooled, the mixture was filtered to obtain a CuInSe ₂ crude product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (d)]. The composition of the product (d) contains 25.44 at % Cu, 26.67 at % In and 47.88 at % Se. Elemental analysis of the black powder showed 0.877 wt% carbon impurity. The X-ray diffraction (XRD) pattern of the black powder [product (d)] is shown in FIG. 2 .

This post-treatment step of product (c) resulted in a significant reduction in the carbon content of _CuInSe2 from 1.536 wt% [product (c)] to 0.877 wt% [product (d)].

Remove impurities of product (d)

5400 mL of 5% nitric acid was added to the reaction tank, and 650 g of product (d) was added while stirring to form a mixture. The mixture was heated to 45°C and stirring was continued for 4 hours. After the workup was complete and the mixture was cooled, the mixture was filtered to obtain the crude _CuInSe2 product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (e)]. The composition of the product (e) contains 26.29 at% Cu, 25.45 at% In and 48.26 at% Se. Elemental analysis of the black powder showed 0.713 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (e)] is shown in FIG. 3 .

<Example 2 (E2)>

Preparation of Quaternary Compound CuInGaSe ₂

350 mL of ethylenediamine was added into the reaction tank, and 6 g of product (a), 11.95 g of product (b) and 1.31 g of Ga ₂ Se ₃ were added while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The mixture was continuously subjected to reflux reaction for 50 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain _CuInGaSe2 crude product. The _CuInGaSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInGaSe ₂ crude product was dried at 150° C. to obtain black powder CuInGaSe ₂ [product (f)]. The composition of the product (k) contains 24.4 at % Cu, 21.6 at % In, 6.48 at % Ga and 47.52 at % Se. Elemental analysis of the black powder showed 1.332 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder CuInGaSe ₂ [product (f)] is shown in FIG. 4 .

Remove impurities of product (f)

200 mL of ethylenediamine was added to the reaction tank, and 15 g of the product (f) and 0.9 g of Se powder were added while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 98 hours in order to subject the product (f) to a work-up step. After the work-up was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSe ₂ product. The _CuInGaSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSe ₂ product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSe ₂ [product (g)]. The composition of the product (g) contains 23.5 at % Cu, 22.28 at % In, 6.49 at % Ga and 47.73 at % Se. Elemental analysis of the black powder showed 0.65% by weight carbon impurity. The X-ray diffraction (XRD) pattern of the black powder [product (g)] is shown in FIG. 5 .

Remove impurities of product (g)

85 mL of 5% nitric acid was added to the reaction tank, and 10 g of the product (g) was further added while stirring to form a mixture. The mixture was heated to 45°C and stirring was continued for 4 hours. After the treatment was completed and the mixture was cooled, the mixture was filtered to obtain a crude _CuInGaSe2 product. The _CuInGaSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSe ₂ product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSe ₂ [product (h)]. The composition of the product (m) contains 23.9 at % Cu, 22.23 at % In, 6.55 at % Ga and 47.32 at % Se. Elemental analysis of the black powder showed 0.511 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (h)] is shown in FIG. 6 .

<Example 3 (E3)>

Preparation of quinary compound CuInGaSeS

350 mL of ethylenediamine was added into the reaction tank, and 6 g of product (b), 8.35 g of In ₂ S ₃ and 1.31 g of Ga ₂ Se ₃ were added while stirring to form a mixture. After stirring the mixture for 5 minutes, the stirring was continued and heated to boiling point. The mixture was continuously subjected to reflux reaction for 50 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSeS product. The CuInGaSeS crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSeS product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSeS [product (i)]. The composition of the product (i) contains 25.4 at% Cu, 19.68 at% In, 6.82 at% Ga, 18.1 at% Se and 30 at% S. Elemental analysis of the black powder showed 0.928% by weight of carbon impurities. The X-ray diffraction (XRD) pattern of the black powder [product (i)] is shown in FIG. 7 .

Remove impurities of product (i)

Add 200 mL of ethylenediamine into the reaction tank, and then add 13 g of product (i) and 0.9 g of Se powder while stirring. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 48 hours to subject the product (i) to a work-up step. After the work-up was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSeS product. The CuInGaSeS crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSeS product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSeS [product (j)]. The composition of the product (j) contains 24.9 at% Cu, 20.1 at% In, 6.7 at% Ga, 18.5 at% Se and 29.8 at% S. Elemental analysis of the black powder showed 0.522 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (j)] is shown in FIG. 8 .

Remove impurities of product (j)

100 mL of 5% nitric acid was added to the reaction tank, and 12 g of product (j) was added while stirring to form a mixture. The mixture was heated to 48°C and stirring was continued for 4 hours. After the treatment was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSeS product. The CuInGaSeS crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSeS product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSeS [product (k)]. The composition of the product (k) contains 24.83 at % Cu, 19.82 at % In, 6.75 at % Ga, 17.41 at % Se and 31.19 at % S. Elemental analysis of the black powder showed 0.331 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (k)] is shown in FIG. 9 .

<Example 4 (E4)>

Preparation of ternary compound CuInSe ₂

600 mL of ethylenediamine was added to the reaction tank, and 18.75 g of Se powder was added while stirring to form a mixture. After stirring this mixture for 5 minutes, 76.24 g of InCl ₃ ·4H ₂ O was added with stirring, and after stirring the mixture in the reaction tank for 20 minutes, 22.64 g of CuCl was further added with stirring. After stirring the mixture in the reaction tank for 20 minutes, the stirring was continued while heating to the boiling point. The mixture was continuously subjected to reflux reaction for 50 hours. After the reaction was complete and the mixture was cooled, the mixture was filtered to obtain _CuInSe2 crude product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (l)]. The composition of the product (1) contains 22.49 at% Cu, 28.99 at% In and 48.51 at% Se. Elemental analysis of the black powder showed 9.216 wt% carbon impurities. The X-ray diffraction (XRD) pattern of the black powder [product (1)] is shown in FIG. 10 .

Remove impurities of product (l)

Add 600 mL of ethylenediamine into the reaction tank, and then add 50 g of product (1) and 1.37 g of Se powder while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 40 hours to subject the product (1) to a work-up step. After the work-up was complete and the mixture was cooled, the mixture was filtered to obtain a crude CuInSe ₂ product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (m)]. The composition of the product (m) contains 22.54 at% Cu, 28.31 at% In and 49.15 at% Se. Elemental analysis of the black powder showed 1.055 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (m)] is shown in FIG. 11 .

The post-treatment step of product (l) resulted in a significant reduction of the carbon content of _CuInSe2 from 9.216 wt% [product (l)] to 1.055 wt% [product (m)].

<Example 5 (E5)>

Preparation of ternary compound CuInSe ₂

170 mL of nitrogen-methylimidazole was added into the reaction tank, 16.6 g of InCl ₃ was added while stirring, and 18.7 g of Na ₂ Se was slowly added while stirring to obtain the first mixture. 90 mL of nitrogen-methylimidazole was added to the second reaction tank, and 7.4 g of CuCl was further added while stirring to obtain a second mixture. The temperature of the first reactant was lowered to 3°C, and then the second reactant was slowly added to the first reactant while stirring, and the temperature of the reaction was controlled below 5°C. The reaction time lasted 12 hours. After the reaction was complete and the mixture was cooled, the mixture was filtered to obtain _CuInSe2 crude product. Wash the _CuInSe2 crude product with a solution containing a large amount of water, 2L of ethanol and 2L of acetone, then dry the cleaned _CuInSe2 crude product at a temperature of 150° C. to obtain a black powder _CuInSe2 [product (n )].

The composition of the product (n) contains 26.02at% Cu, 26.34at% In and 47.64at% Se. Elemental analysis of the black powder showed 4.322 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (n)] is shown in FIG. 12 .

Remove impurities from product (n)

Add 80 mL of ethylenediamine into the reaction tank, and then add 9 g of product (n) and 0.25 g of Se powder while stirring. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 45 hours in order to work up the product (n). After the work-up step was completed and the mixture was cooled, the mixture was filtered to obtain the crude _CuInSe2 product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (o)]. The composition of the product (o) contains 25.68 at% Cu, 26.13 at% In and 48.19 at% Se. Elemental analysis of the black powder showed 0.912 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (o)] is shown in FIG. 13 .

This post-treatment step of product (n) resulted in a significant reduction in the carbon content of _CuInSe2 from 4.322 wt% [product (n)] to 0.912 wt% [product (o)].

<Example 6 (E6)>

Preparation of Quaternary Compound CuInGaSe ₂

Add 170 mL of nitrogen-methylimidazole into the reaction tank, add 14.6 g of InCl ₃ and 1.58 g of GaCl ₃ while stirring, and slowly add 18.7 g of Na ₂ Se while stirring to obtain the first mixture. 90 mL of nitrogen-methylimidazole was added to the second reaction tank, and 7.4 g of CuCl was further added while stirring to obtain a second mixture. The temperature of the first reactant was lowered to 3°C, and then the second reactant was slowly added to the first reactant while stirring, and the temperature of the reaction was controlled below 5°C. The reaction time lasted 12 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain _CuInGaSe2 crude product. Wash the _CuInGaSe2 crude product with a solution containing a large amount of water, 2L of ethanol and 2L of acetone, then dry the cleaned _CuInGaSe2 crude product at a temperature of 150°C to obtain a black powder _CuInGaSe2 [product (p )].

The composition of the product (p) contains 19.4 at % Cu, 21.72 at % In, 7.28 at % Ga and 51.6 at % Se. Elemental analysis of the black powder showed 4.339 wt% carbon impurities therein. The X-ray diffraction (XRD) pattern of the black powder [product (p)] is shown in FIG. 14 .

Remove impurities of product (p)

Add 105 mL of ethylenediamine into the reaction tank, and then add 12 g of product (p) and 0.33 g of Se powder while stirring. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 40 hours to subject the product (f) to a work-up step. After the work-up was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSe ₂ product. The _CuInGaSe2 crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The washed CuInGaSe ₂ crude product was dried at 150° C. to obtain black powder CuInGaSe ₂ [product (q)]. The composition of the product (q) contains 18.42 at% Cu, 22.25 at% In, 7.41 at% Ga and 51.92 at% Se. Elemental analysis of the black powder showed 0.872 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (q)] is shown in FIG. 15 .

This post-treatment step of product (p) resulted in a significant reduction in the carbon content of _CuInGaSe2 from 4.339 wt% [product (p)] to 0.872 wt% [product (q)].

<Example 7 (E7)>

Preparation of quinary compound CuInGaSeS

Add 170mL of nitrogen-methylimidazole into the reaction tank, add 14.6g of InCl ₃ and 1.58g of GaCl ₃ while stirring, and slowly add 9.37g of Na ₂ Se powder and 5.85g of Na ₂ S while stirring , to obtain the first mixture. 90 mL of nitrogen-methylimidazole was added to the second reaction tank, and 7.4 g of CuCl was further added while stirring to obtain a second mixture. The temperature of the first reactant was lowered to 3°C, and then the second reactant was slowly added to the first reactant while stirring, and the temperature of the reaction was controlled below 5°C. The reaction time lasted 12 hours. After the reaction was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSeS product. The CuInGaSeS crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, and then the washed CuInGaSeS crude product was dried at 150° C. to obtain black powder CuInGaSeS [product (r)].

The composition of the product (r) contains 24.64 at% Cu, 22.1 at% In, 6.98 at% Ga, 25.88 at% Se and 20.4 at% S. Elemental analysis of the black powder showed 2.936 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (r)] is shown in FIG. 16 .

Remove impurities of product (r)

90 mL of ethylenediamine was added into the reaction tank, and 10 g of product (r) and 0.28 g of Se powder were added while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The product (r) was subjected to a work-up step, and the mixture was kept at reflux for 40 hours. After the work-up was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInGaSeS product. The CuInGaSeS crude product was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone. The crude CuInGaSeS product after washing was dried at a temperature of 150° C. to obtain black powder CuInGaSeS [product (s)]. The composition of the product (s) contained 24.25 at% Cu, 22.1 at% In, 7.11 at% Ga, 26.37 at% Se and 19.38 at% S. Elemental analysis of the black powder showed 0.917 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (s)] is shown in FIG. 17 .

This post-treatment step of product (r) resulted in a significant reduction in the carbon content of CuInGaSeS from 2.936 wt% [product (r)] to 0.917 wt% [product (s)].

<Example 8 (E8)>

Preparation of ternary compound CuInSe ₂

150 mL of ethylenediamine was added to the reaction tank, and 2.63 g of Se powder was added while stirring to form a mixture. After stirring the mixture for 5 minutes, 10.05 g of In(NO ₃ ) ₃ was added while stirring, and after stirring the mixture in the reaction tank for 15 minutes, 6.9 g of Cu(NO ₃ ) ₂ was further added while stirring. After stirring the mixture in the reaction tank for 10 minutes, the stirring was continued while heating to the boiling point. The mixture was continuously subjected to reflux reaction for 45 hours, and after the reaction was completed and the mixture was cooled, the mixture was filtered to obtain a crude CuInSe ₂ product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (t)]. The composition of the product (t) contains 25.72 at % Cu, 26.83 at % In and 47.45 at % Se. Elemental analysis of the black powder showed 3.255 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (t)] is shown in FIG. 18 .

Remove impurities from product (t)

80 mL of ethylenediamine was added to the reaction tank, and 10 g of the product (t) and 0.28 g of Se powder were added while stirring to form a mixture. After stirring the mixture in the reaction tank for 3 minutes, the stirring was continued while heating to the boiling point. The reaction mixture was continued at reflux for 45 hours in order to work up the product (t). After the work-up was complete and the mixture was cooled, the mixture was filtered to obtain a crude CuInSe ₂ product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (u)]. The composition of the product (u) contains 25.64 at % Cu, 26.72 at % In and 47.64 at % Se. Elemental analysis of the black powder showed 0.912 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (u)] is shown in FIG. 19 .

<Comparative Example 1 (CE1)>

Preparation of ternary compound CuInSe ₂

700 mL of ethylenediamine was added into the reaction tank, and 12 g of Cu ₂ Se, 27.2 g of In ₂ Se ₃ and 2.38 g of Se powder were added while stirring to form a mixture. After stirring the mixture for 5 minutes, the stirring was continued and heated to boiling point. The mixture was continuously subjected to reflux reaction for 55 hours, and after the reaction was completed and the mixture was cooled, the mixture was filtered to obtain CuInSe ₂ crude product and a relatively large yield of red fine powder. The red fine powder has a relatively small particle size, so it is not easy to separate the red fine powder by filtering the mixture. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (v)]. The composition of the product (v) contains 24.48 at % Cu, 26.8 at % In and 48.72 at % Se. Elemental analysis of the black powder showed 2.239 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (v)] is shown in FIG. 20 .

<Comparative Example 2 (CE2)>

Preparation of ternary compound CuInSe ₂

Add 600 mL of ethylenediamine into the reaction tank, and then add 46.3 g of Se powder while stirring. After stirring for 5 minutes, add 76.24 g of InCl ₃ ·4H ₂ O while stirring to form a mixture. After stirring the mixture in the reaction tank for 20 minutes, 22.64 g of CuCl was further added while stirring. After stirring for 20 minutes, continue to stir and heat to boiling point. The mixture was continuously subjected to reflux reaction for 50 hours, and after the reaction was completed and the mixture was cooled, the mixture was filtered to obtain CuInSe ₂ crude product and a relatively large yield of red fine powder. The red fine powder has a relatively small particle size, so it is not easy to separate the red fine powder by filtering the mixture. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (w)]. The composition of the product (w) contains 24.37 at% Cu, 28.19 at% In and 47.44 at% Se. Elemental analysis of the black powder showed 8.526 wt% carbon impurities. The X-ray diffraction (XRD) pattern of the black powder [product (w)] is shown in FIG. 21 .

<Comparative example 3 (CE3)>

Blank test: Treatment of _CuInSe2 without Se powder

130 mL of ethylenediamine was added to the reaction tank, and 20 g of CuInSe ₂ (carbon impurity content: 8.526 wt %) was further added while stirring to form a mixture. After stirring the mixture in the reaction tank for 5 minutes, the stirring was continued while heating to the boiling point. The mixture was continuously subjected to reflux reaction for 55 hours, and after the reaction was completed and the mixture was cooled, the mixture was filtered to obtain CuInSe ₂ crude product. The _CuInSe2 crude product was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone. The washed CuInSe ₂ crude product was dried at 150° C. to obtain black powder CuInSe ₂ [product (x)]. The composition of the product (x) contains 26.71 at% Cu, 25.59 at% In and 47.7 at% Se. Elemental analysis of the black powder showed 2.012 wt% carbon impurity therein. The X-ray diffraction (XRD) pattern of the black powder [product (x)] is shown in FIG. 22 .

The difference between Comparative Example 1 and Example 1 is that in Comparative Example 1, Se powder was added to the reaction mixture formed by Cu ₂ Se and In ₂ Se ₃ . The result shows that the black powder CuInSe ₂ [product (v)] that comparative example 1 produces, its carbon content is higher than the product (c) without aftertreatment in embodiment 1, is obviously higher than in embodiment 1 again The post-treatment product (d); it can be seen that the additional Se powder added to the reaction mixture cannot achieve the effect of reducing the carbon content produced by the post-treatment of Example 1.

The difference between Comparative Example 2 and Example 4 is that in Comparative Example 2, a larger amount of Se powder is added to the reaction mixture formed by Cu ₂ Se and In ₂ Se ₃ . The result shows, the black powder CuInSe that comparative example 2 produces ₂ [product (w)], its carbon content is slightly lower than the product (l) without aftertreatment in embodiment 4, but obviously higher than in embodiment 4 The post-treatment product (m); it can be seen that adding a relatively large amount of Se powder to the reaction mixture cannot achieve the effect of reducing the carbon content produced by the post-treatment in Example 4.

The difference between Comparative Example 3 and the foregoing Examples 1 and 4 is that, in Comparative Example 3, no Se powder was used when post-processing CuInSe ₂ . The results show that the black powder CuInSe ₂ [product (x)] produced in Comparative Example 3 has an increased carbon content after post-treatment. It can be seen that the post-treatment step without using Se powder cannot reduce carbon impurities. content.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this field Those skilled in the art, without departing from the scope of the technical solution of the present invention, may use the technical content disclosed above to make some changes or modify them into equivalent embodiments with equivalent changes, but as long as they do not depart from the technical solution of the present invention, the Technical Essence Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

Claims (13)

1. a manufacture method of chalcopyrite type compound, is characterized in that it comprises the following steps: Make the reaction mixture carry out reflux reaction in the first solvent; The reacted reaction mixture is filtered to obtain a crude product of a chalcopyrite-type compound; mixing the crude product, the second solvent, and a post-treatment material to form a treatment mixture, the post-treatment material being selected from S, Se, Te, or any combination thereof; and The workup mixture is heated under reflux conditions to remove impurities from the crude product in a manner that allows workup of the crude product to produce a chalcopyrite-type compound containing M ¹ , M ² and A, M ¹ is selected from Cu, Au, Ag, Na, Li or K, the ^M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or any combination of the foregoing, and the A is selected from From S, Se, Te or any combination of the foregoing. 2. the manufacture method of chalcopyrite type compound as claimed in claim 1, is characterized in that: this first solvent and this second solvent are each independently selected from alkylamine, dimethylformamide, nitrogen- Methyltetrahydropyrrolone, Methimidazole, Dimethylsulfoxide, Oleylamine, Glycerin, or Ethylene Glycol. 3 . The method for producing chalcopyrite-type compounds as claimed in claim 2 , wherein the first solvent and the second solvent are each independently selected from ethylenediamine or methylimidazole. 4 . 4. the manufacture method of chalcopyrite type compound as claimed in claim 1, is characterized in that: this manufacture method also comprises a cleaning step before forming this treatment mixture, and this cleaning step is by using cleaning solution to wash this crude product , the cleaning solution includes water, alcohol and acetone. 5. the manufacture method of chalcopyrite type compound as claimed in claim 1, is characterized in that: this manufacture method also comprises a step, and this step is to filter the reaction mixture through aftertreatment and obtain the crude product through processing, Then, the treated crude product is washed with a washing solution including water, alcohol and acetone. 6. The method for producing chalcopyrite-type compounds as claimed in claim 5, characterized in that: the production method further comprises a step of washing the treated crude product with an acid solution. 7. the manufacture method of chalcopyrite type compound as claimed in claim 1, is characterized in that: The reaction mixture comprises at least one first compound and at least one second compound, the first compound includes M ¹ and A ¹ , the second compound includes M ² and A ¹ , the A ¹ is selected from S, Se, Te , Cl ^- , Br ^- , I ^- , OH ^- , NO ₃ ^- , SO ₄ ^2- , CH ₃ COO ^- , acetylacetonate ion or any combination of S, Se and Te; and When A ¹ of the first compound and the second compound is selected from Cl ^- , Br ^- , I ^- , OH ^- , NO ₃ ^- , SO ₄ ^2- , CH ₃ COO ^- or acetylacetonate ion, the The reaction mixture also includes a powder selected from S, Se, Te or any combination thereof. 8 . The method for producing chalcopyrite-type compounds as claimed in claim 7 , wherein the reaction mixture contains Cu ₂ Se and In ₂ Se ₃ . 9 . The method for producing chalcopyrite-type compounds as claimed in claim 7 , wherein the reaction mixture comprises Cu ₂ Se, In ₂ Se ₃ and Ga ₂ Se ₃ . 10 . The method for producing chalcopyrite-type compounds as claimed in claim 7 , wherein the reaction mixture comprises Cu ₂ Se, In ₂ S ₃ and Ga ₂ Se ₃ . 11 . The method for producing chalcopyrite-type compounds as claimed in claim 7 , wherein the reaction mixture comprises Se, InCl ₃ .4H ₂ O and CuCl. 12. The method for producing chalcopyrite-type compounds as claimed in claim 7, wherein the reaction mixture comprises InCl ₃ , Na ₂ Se and CuCl. 13. The method for producing chalcopyrite-type compounds as claimed in claim 7, wherein the reaction mixture comprises InCl ₃ , GaCl ₃ , Na ₂ Se and CuCl.

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