CN102649543A - Manufacture method of chalcopyrite type compounds - Google Patents
Manufacture method of chalcopyrite type compounds Download PDFInfo
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- CN102649543A CN102649543A CN2011100460444A CN201110046044A CN102649543A CN 102649543 A CN102649543 A CN 102649543A CN 2011100460444 A CN2011100460444 A CN 2011100460444A CN 201110046044 A CN201110046044 A CN 201110046044A CN 102649543 A CN102649543 A CN 102649543A
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Abstract
The invention relates to a manufacture method of chalcopyrite type compounds. The manufacture method comprises the following steps that: reaction mixtures are subjected to reflux reaction in a first solvent, the filtering is carried out after reaction, and crude products of the chalcopyrite type compounds are obtained; the crude products, a second solvent and post-treatment materials are mixed to form treated mixtures; and the treated mixtures are heated in a mode of allowing the post-treatment of the crude products under the reflux condition for removing impurities from the crude products, the chalcopyrite type compounds containing M1, M2 and A are generated, M1 is selected from Cu, Au, Ag, Na, Li or K, M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn or Mg or any combination of In, Ga, Al, Ti, Zn, Cd, Sn and Mg, and A is selected from S, Se or Te or any combination of S, Se and Te. Therefore, through the manufacture method provided by the invention, the impurity content in the chalcopyrite type compounds can be reduced.
Description
Technical field
The present invention relates to a kind of method of manufacture of chalcopyrite type cpd, particularly relate to a kind of method of manufacture of chalcopyrite type cpd of the aftertreatment that comprises crude product.
Background technology
Chalcopyrite type cpd, for example CuInSe
2, Cu (In
xGa
1-x) (Se
yS
2-y) and Cu (In
xAl
1-x) (Se
yS
2-y), because of possessing the semi-conductor adsorption layer that advantages such as high photoelectric efficiency and low cost often are used to make solar cell.Contained impurity content in the chalcopyrite type cpd, carbon content for example can cause significant negative impact to the photoelectric efficiency of chalcopyrite type cpd, and therefore expectation can produce the chalcopyrite type cpd with low impurity content.
Li Bin people such as (Bin Li) is at Adv.Mater., and 1999,11, No.17,1456-1459 disclose one and have made CuInSe
2Molten heat (solvothermal) compound method of nano material.This method comprises makes CuCl
22H
2O, InCl
34H
2The mixture that O and Se powder are formed reacted 15 hours under quadrol solvent and 180 ℃ of temperature, to form throw out.The aqueous solution that this throw out utilization contains ethanol and water cleans; To remove the by product in this throw out; Then carry out drying again, the chalcopyrite type cpd powder that has the yellow copper ore phase structure with formation, but this chalcopyrite type cpd powder has higher carbon impurity content.
USP announces the 7th, 591, No. 990, discloses a kind of manufacturing and has M
3M
1A
2The processing procedure of the chalcopyrite type cpd of molecular formula, M
1Can be selected from Al
3+, Ga
3+Or In
3+Deng, M
3Can be selected from Cu
+Or Ag
+Deng, and A can be selected from S, Se or Te.This manufacture craft comprises order and has molecular formula M
3The compound of X with have a molecular formula M
2M
1A
2Compound in ligand solvent, react, have molecular formula M with formation
3M
1A
2Chalcopyrite type cpd, X can be halogen atom, M
2Can be Li
+, Na
+, K
+Deng.Also has quite high impurity content with the prepared chalcopyrite type cpd of this manufacture craft.
This shows that the method for manufacture of above-mentioned existing chalcopyrite type cpd obviously still has inconvenience and defective, and demands urgently further improving in method and use.In order to solve the problem of above-mentioned existence; Relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly; But do not see always that for a long time suitable design is developed completion, and general method does not have appropriate method to address the above problem, this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of method of manufacture of new chalcopyrite type cpd, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.
Summary of the invention
The objective of the invention is to; Overcome the defective of the method for manufacture existence of existing chalcopyrite type cpd; And a kind of method of manufacture of new chalcopyrite type cpd is provided, technical problem to be solved is to make its content that can reduce impurity in the chalcopyrite type cpd, is very suitable for practicality.The object of the invention and solve its technical problem and adopt following technical scheme to realize.The method of manufacture of a kind of chalcopyrite type cpd that proposes according to the present invention comprises and makes reaction mixture in first solvent, carry out back flow reaction; Reacted reaction mixture is filtered and obtain the chalcopyrite type cpd crude product; This crude product, second solvent are mixed with material after-treatment and form treating mixt, and this material after-treatment is to be selected from S, Se, Te or aforesaid arbitrary combination; And make this treating mixt be able to allow this crude product to carry out the mode of aftertreatment remove under the reflux conditions of impurity to heat, contain M with generation at this crude product certainly
1, M
2And the chalcopyrite type cpd of A, M
1Be to be selected from Cu, Au, Ag, Na, Li or K, this M
2Be to be selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or aforesaid arbitrary combination, and this A is selected from S, Se, Te or aforesaid arbitrary combination.
The object of the invention and solve its technical problem and also can adopt following technical measures further to realize.
Preferably; The method of manufacture of aforesaid chalcopyrite type cpd, wherein said first solvent and this second solvent are to be selected from alkylamine, N, nitrogen-methyl Pyrrolidine ketone, Methylimidazole, methyl-sulphoxide, oleyl amine, glycerine or terepthaloyl moietie independently of one another.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said first solvent and this second solvent are to be selected from quadrol or Methylimidazole independently of one another.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd also comprises a cleaning step before forming this treating mixt, and this cleaning step is to clean this crude product through the use cleaning solution, and this cleaning solution comprises water, alcohol and acetone.
Preferably; The method of manufacture of aforesaid chalcopyrite type cpd also comprises a step, and this step is to obtain treated crude product with filtering through the reaction mixture of aftertreatment; Then clean this treated crude product with cleaning solution again, this cleaning solution comprises water, alcohol and acetone.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd also comprises the step of cleaning this treated crude product with acid solution.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises at least one first compound and at least one second compound, and this first compound comprises M
1And A
1, this second compound comprises M
2And A
1, this A
1Be to be selected from S, Se, Te, Cl
-, Br
-, I
-, OH
-, NO
3 -, SO
4 2-, CH
3COO
-, methyl ethyl diketone acid ion or S, Se and Te arbitrary combination; Reach A when this first compound and this second compound
1Be to be selected from Cl
-, Br
-, I
-, OH
-, NO
3 -, SO
4 2-, CH
3COO
-Or during the methyl ethyl diketone acid ion, this reaction mixture also comprises powder, and this powder is to be selected from S, Se, Te or aforesaid arbitrary combination.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises Cu
2Se and In
2Se
3
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises Cu
2Se, In
2Se
3And Ga
2Se
3
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises Cu
2Se, In
2S
3And Ga
2Se
3
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises Se, InCl
34H
2O and CuCl.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises InCl
3, Na
2Se and CuCl.
Preferably, the method for manufacture of aforesaid chalcopyrite type cpd, wherein said reaction mixture comprises InCl
3, GaCl
3, Na
2Se and CuCl.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, the method for manufacture of chalcopyrite type cpd of the present invention has advantage and beneficial effect at least: method of manufacture of the present invention can reduce the content of impurity in the chalcopyrite type cpd.
In sum, the invention relates to a kind of method of manufacture of chalcopyrite type cpd, comprise and make reaction mixture in first solvent, carry out back flow reaction, filter after the reaction and obtain the chalcopyrite type cpd crude product; This crude product, second solvent are mixed with material after-treatment and form treating mixt; And this treating mixt is removed at this crude product certainly to allow this crude product to carry out the mode of aftertreatment heat under the reflux conditions of impurity, contain M with generation
1, M
2And the chalcopyrite type cpd of A, M
1Be to be selected from Cu, Au, Ag, Na, Li or K, this M
2Be to be selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or aforesaid arbitrary combination, and this A is selected from S, Se, Te or aforesaid arbitrary combination.The present invention has obvious improvement technically, and has tangible positively effect, really is the new design of a novelty, progress, practicality.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention; Understand technique means of the present invention in order can more to know; And can implement according to the content of specification sheets, and for let of the present invention above-mentioned with other purposes, feature and advantage can be more obviously understandable, below special act preferred embodiment; And conjunction with figs., specify as follows.
Description of drawings
Fig. 1 is the X ray diffraction chart of illustrative embodiment 1 prepared product without aftertreatment (c).
Fig. 2 is the X ray diffraction chart of illustrative embodiment 1 prepared product through aftertreatment (d).
Fig. 3 is that illustrative embodiment 1 is prepared through aftertreatment and with the X ray diffraction chart of the product (e) of an acid cleaning.
Fig. 4 is the X ray diffraction chart of illustrative embodiment 2 prepared products without aftertreatment (f).
Fig. 5 is the X ray diffraction chart of illustrative embodiment 2 prepared products through aftertreatment (g);
Fig. 6 is that illustrative embodiment 2 is prepared through aftertreatment and with the X ray diffraction chart of the product (h) of acid solution cleaning.
Fig. 7 is the X ray diffraction chart of illustrative embodiment 3 prepared products without aftertreatment (i).
Fig. 8 is the X ray diffraction chart of illustrative embodiment 3 prepared products through aftertreatment (j).
Fig. 9 is that illustrative embodiment 3 is prepared through aftertreatment and with the X ray diffraction chart of the product (k) of an acid cleaning.
Figure 10 is the X ray diffraction chart of illustrative embodiment 4 prepared products without aftertreatment (l).
Figure 11 is the X ray diffraction chart of illustrative embodiment 4 prepared products through aftertreatment (m).
Figure 12 is the X ray diffraction chart of illustrative embodiment 5 prepared products without aftertreatment (n).
Figure 13 is the X ray diffraction chart of illustrative embodiment 5 prepared products through aftertreatment (o).
Figure 14 is the X ray diffraction chart of illustrative embodiment 6 prepared products without aftertreatment (p).
Figure 15 is the X ray diffraction chart of illustrative embodiment 6 prepared products through aftertreatment (q).
Figure 16 is the X ray diffraction chart of illustrative embodiment 7 prepared products without aftertreatment (r).
Figure 17 is the X ray diffraction chart of illustrative embodiment 7 prepared products through aftertreatment (s).
Figure 18 is the X ray diffraction chart of illustrative embodiment 8 prepared products without aftertreatment (t).
Figure 19 is the X ray diffraction chart of illustrative embodiment 8 prepared products through aftertreatment (u).
Figure 20 is explanation comparative example 1 a prepared product (X ray diffraction chart v).
Figure 21 is the X ray diffraction chart of explanation comparative example 2 prepared products (w).
Figure 22 is the X ray diffraction chart of explanation comparative example 3 prepared products (x).
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention; Below in conjunction with accompanying drawing and preferred embodiment; To its embodiment of method of manufacture, method, step, characteristic and the effect thereof of the chalcopyrite type cpd that proposes according to the present invention, specify as after.
Relevant aforementioned and other technology contents, characteristics and effect of the present invention can be known to appear in the following detailed description that cooperates with reference to graphic preferred embodiment.Through the explanation of embodiment, when can being to reach technique means that predetermined purpose takes and effect to obtain one more deeply and concrete understanding to the present invention, yet the appended graphic usefulness that only provides reference and explanation be not to be used for the present invention is limited.
The preferred embodiment of the method for manufacture of chalcopyrite type cpd of the present invention comprises and makes reaction mixture in first solvent, carry out back flow reaction; Reacted reaction mixture is filtered and obtain the chalcopyrite type cpd crude product; This crude product, second solvent are mixed with material after-treatment and form treating mixt, and this material after-treatment is to be selected from S, Se, Te or aforesaid arbitrary combination; And make this treating mixt be able to allow this crude product to carry out the mode of an aftertreatment remove under the reflux conditions of impurity to heat, contain M with generation at this crude product certainly
1, M
2And the chalcopyrite type cpd of A, M
1Be to be selected from Cu, Au, Ag, Na, Li or K, this M
2Be to be selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or aforesaid arbitrary combination, and this A is selected from S, Se, Te or aforesaid arbitrary combination.
This reaction mixture comprises at least one first compound and at least one second compound, and this first compound comprises M
1And A
1, this second compound comprises M
2And A
1, this A
1Be to be selected from S, Se, Te, Cl
-, Br
-, I
-, OH
-, NO
3 -, SO
4 2-, CH
3COO
-, methyl ethyl diketone acid ion or S, Se and Te arbitrary combination.
A when this first compound and second compound
1Be not S, Se, Te, or during the arbitrary combination of S, Se and Te, this reaction mixture also comprises powder, this powder is to be selected from S, Se, Te or aforesaid arbitrary combination.
In preferred embodiment of the present invention; This method of manufacture is with this crude product, second solvent and before the aftertreatment powder mixes; Also comprise with cleaning solution and clean this treated crude product, this cleaning solution comprises water, alcohol and acetone, then dry again this treated crude product.
Preferably, in preferred embodiment of the present invention, after this method of manufacture also was included in this aftertreatment, the crude product with this chalcopyrite type cpd of acid solution cleaning then cleaned this crude product with this cleaning solution again, and dry this crude product.
Be applicable to first solvent of the present invention and second solvent for example alkylamine, N (DMF), nitrogen-methyl Pyrrolidine ketone (NMP), Methylimidazole, methyl-sulphoxide (DMSO), oleyl amine, glycerine or terepthaloyl moietie etc.In preferred embodiment of the present invention, this first solvent and this second solvent are to be selected from quadrol or Methylimidazole independently of one another.
The suitable example of the acid that is contained in this acid solution comprises nitric acid, hydrochloric acid, Hydrocerol A, acetic acid, phosphoric acid, sulfuric acid and oxalic acid.Preferably, when the acid of selecting for use was strong acid, the concentration range of this strong acid was 5～10wt%.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment is merely and illustrates usefulness, and should not be interpreted as the restriction that the present invention implements.
< embodiment 1 (E1) >
Preparation In
2Se
3
The quadrol of 4000mL is added in the reactive tank, while stir the Se powder that adds 302.5g again, wait to stir 5 minutes after, while stir the InCl that adds 750.5g lentamente
34H
2O is to form mixture.Mixture in this reactive tank was stirred after 20 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 30 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain In
2Se
3Crude product.Clean this In with solution
2Se
3Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the In after the cleaning
2Se
3Crude product carries out drying under 150 ℃ of temperature, obtain yellow powder In
2Se
3[product (a)].The composition of this product (a) contains the In of 42.63at% and the Se of 57.37at%.This yellow powder is carried out ultimate analysis, show the carbon impurity that wherein contains 4.81wt%.
Preparation Cu
2Se
The quadrol of 5500mL is added in the reactive tank, stirs the Se powder that adds 231g more on one side, wait to stir 5 minutes after, while stir the CuCl that adds 580g lentamente, with the formation mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 24 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain Cu
2The Se crude product.Clean this Cu with solution
2Se crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the Cu after the cleaning
2The Se crude product carries out drying under 150 ℃ of temperature, obtain mazarine powder Cu
2Se [product (b)].The composition of this product (b) contains the Cu of 63.82at% and the Se of 36.18at%.This mazarine powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.1wt%.
Preparation ternary compound CuInSe
2
The quadrol of 9000mL is added in the reactive tank, stir the product (a) that adds 600g again and the product (b) of 260g on one side, with the formation mixture.Wait to stir this mixture after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 30 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain a CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (c)].The composition of this product (c) contains the Cu of 25.43a t%, the In of 26.68at% and the Se of 47.89at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 1.536wt%.X-ray diffraction (XRD) figure of this black powder [product (c)] is as shown in Figure 1.
Remove the impurity of product (c)
The quadrol of 6000mL is added in the reactive tank, stir the product (c) that adds 730g again and the Se powder of 44g on one side, with the acquisition mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 40 hours, so that product (c) is carried out post-processing step.After post-processing step is accomplished and treated this mixture cooling, filter this mixture, to obtain a CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (d)].The composition of this product (d) contains the Cu of 25.44at%, the In of 26.67at% and the Se of 47.88at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.877wt%.X-ray diffraction (XRD) figure of this black powder [product (d)] is as shown in Figure 2.
The post-processing step of this product (c) makes CuInSe
2Carbon content obviously be reduced to 0.877wt% [product (d)] from 1.536wt% [product (c)].
Remove the impurity of product (d)
5% nitric acid of 5400mL is added in the reactive tank,, form mixture while stir the product (d) that adds 650g again.With this mixture heating up to 45 ℃ also lasting stirring 4 hours.After finishing dealing with and treating this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (e)].The composition of this product (e) contains the Cu of 26.29at%, the In of 25.45at% and the Se of 48.26at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.713wt%.X-ray diffraction (XRD) figure of this black powder [product (e)] is as shown in Figure 3.
< embodiment 2 (E2) >
Preparation quaternary compound CuInGaSe
2
The quadrol of 350mL is added in the reactive tank, while stir the product (a) that adds 6g again, the product (b) of 11.95g and the Ga of 1.31g
2Se
3, form mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 50 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInGaSe
2Crude product.Clean this CuInGaSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (f)].The composition of this product (k) contains the Cu of 24.4at%, the In of 21.6at%, the Ga of 6.48at% and the Se of 47.52at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 1.332wt%.This black powder CuInGaSe
2X-ray diffraction (XRD) figure of [product (f)] is as shown in Figure 4.
Remove the impurity of product (f)
The quadrol of 200mL is added in the reactive tank, stir the product (f) that adds 15g again and the Se powder of 0.9g on one side, the formation mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 98 hours, so that product (f) is carried out post-processing step.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInGaSe
2Crude product.Clean this CuInGaSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (g)].The composition of this product (g) contains the Cu of 23.5at%, the In of 22.28at%, the Ga of 6.49at% and the Se of 47.73at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.65wt%.X-ray diffraction (XRD) figure of this black powder [product (g)] is as shown in Figure 5.
Remove the impurity of product (g)
5% nitric acid of 85mL is added in the reactive tank,, form mixture while stir the product (g) that adds 10g again.With this mixture heating up to 45 ℃ also lasting stirring 4 hours.After finishing dealing with and treating this mixture cooling, filter this mixture, to obtain CuInGaSe
2Crude product.Clean this CuInGaSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (h)].The composition of this product (m) contains the Cu of 23.9at%, the In of 22.23at%, the Ga of 6.55at% and the Se of 47.32at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.511wt%.X-ray diffraction (XRD) figure of this black powder [product (h)] is as shown in Figure 6.
< embodiment 3 (E3) >
Prepare five yuan of Compound C uInGaSeS
The quadrol of 350mL is added in the reactive tank, while stir the product (b) that adds 6g again, the In of 8.35g
2S
3And 1.31g Ga
2Se
3, form mixture.Wait to stir this mixture after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 50 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain the CuInGaSeS crude product.Clean this CuInGaSeS crude product with solution, this solution contains the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSeS crude product after the cleaning under 150 ℃ of temperature, carry out drying, obtain black powder CuInGaSeS [product (i)].The composition of this product (i) contains the Cu of 25.4at%, the In of 19.68at%, the Ga of 6.82at%, the Se of 18.1at% and the S of 30at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.928wt%.X-ray diffraction (XRD) figure of this black powder [product (i)] is as shown in Figure 7.
Remove the impurity of product (i)
The quadrol of 200mL is added in the reactive tank, while stir the product (i) that adds 13g again and the Se powder of 0.9g.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 48 hours, so that product (i) is carried out post-processing step.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain the CuInGaSeS crude product.Clean this CuInGaSeS crude product with solution, this solution contains the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSeS crude product after the cleaning under 150 ℃ of temperature, carry out drying, obtain black powder CuInGaSeS [product (j)].The composition of this product (j) contains the Cu of 24.9at%, the In of 20.1at%, the Ga of 6.7at%, the Se of 18.5at% and the S of 29.8at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.522wt%.X-ray diffraction (XRD) figure of this black powder [product (j)] is as shown in Figure 8.
Remove the impurity of product (j)
5% nitric acid of 100mL is added in the reactive tank,, form mixture while stir the product (j) that adds 12g again.With this mixture heating up to 48 ℃ also lasting stirring 4 hours.After finishing dealing with and treating this mixture cooling, filter this mixture, to obtain the CuInGaSeS crude product.Clean this CuInGaSeS crude product with solution, this solution contains the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSeS crude product after the cleaning under 150 ℃ of temperature, carry out drying, obtain black powder CuInGaSeS [product (k)].The composition of this product (k) contains the Cu of 24.83at%, the In of 19.82at%, the Ga of 6.75at%, the Se of 17.41at% and the S of 31.19at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.331wt%.X-ray diffraction (XRD) figure of this black powder [product (k)] is as shown in Figure 9.
< embodiment 4 (E4) >
Preparation ternary compound CuInSe
2
The quadrol of 600mL is added in the reactive tank,, form mixture while stir the Se powder that adds 18.75g again.Stir this mixture after 5 minutes, while stir the InCl that adds 76.24g
34H
2O stirs after 20 minutes, while stir the CuCl that adds 22.64g again the mixture in this reactive tank.Mixture in this reactive tank was stirred after 20 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 50 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (l)].The composition of this product (l) contains the Cu of 22.49at%, the In of 28.99at% and the Se of 48.51at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 9.216wt%.X-ray diffraction (XRD) figure of this black powder [product (l)] is shown in figure 10.
Remove the impurity of product (l)
The quadrol of 600mL is added in the reactive tank, stir the product (l) that adds 50g again and the Se powder of 1.37g on one side, the formation mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 40 hours, so that product (l) is carried out post-processing step.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (m)].The composition of this product (m) contains the Cu of 22.54at%, the In of 28.31at% and the Se of 49.15at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 1.055wt%.X-ray diffraction (XRD) figure of this black powder [product (m)] is shown in figure 11.
The post-processing step of product (l) makes CuInSe
2Carbon content obviously be reduced to 1.055wt% [product (m)] from 9.216wt% [product (l)].
< embodiment 5 (E5) >
Preparation ternary compound CuInSe
2
Nitrogen-Methylimidazole of 170mL is added in the reactive tank, while stir the InCl that adds 16.6g
3While, stir the Na that adds 18.7g more lentamente
2Se obtains first mixture.In second reactive tank, add nitrogen-Methylimidazole of 90mL,, obtain second mixture while stir the CuCl that adds 7.4g again.This first reactant is cooled to 3 ℃, this second reactant is added in this first reactant, and the temperature of reaction is controlled at below 5 ℃ while stir subsequently lentamente.This reaction times continues 12 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L, the CuInSe after then will cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (n)].
The composition of this product (n) contains the Cu of 26.02a t%, the In of 26.34at% and the Se of 47.64at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 4.322wt%.X-ray diffraction (XRD) figure of this black powder [product (n)] is shown in figure 12.
Remove the impurity of product (n)
The quadrol of 80mL is added in the reactive tank, while stir the product (n) that adds 9g again and the Se powder of 0.25g.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 45 hours, so that product (n) is carried out post-processing step.After post-processing step is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (o)].The composition of this product (o) contains the Cu of 25.68at%, the In of 26.13at% and the Se of 48.19at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.912wt%.X-ray diffraction (XRD) figure of this black powder [product (o)] is shown in figure 13.
The post-processing step of this product (n) makes CuInSe
2Carbon content obviously be reduced to 0.912wt% [product (o)] from 4.322wt% [product (n)].
< embodiment 6 (E6) >
Preparation quaternary compound CuInGaSe
2
Nitrogen-Methylimidazole of 170mL is added in the reactive tank, while stir the InCl that adds 14.6g
3And the GaCl of 1.58g
3While, stir the Na that adds 18.7g more lentamente
2Se obtains first mixture.In second reactive tank, add nitrogen-Methylimidazole of 90mL,, obtain second mixture while stir the CuCl that adds 7.4g again.This first reactant is cooled to 3 ℃, this second reactant is added in this first reactant, and the temperature of reaction is controlled at below 5 ℃ while stir subsequently lentamente.This reaction times continues 12 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInGaSe
2Crude product.Clean this CuInGaSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L, the CuInGaSe after then will cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (p)].
The composition of this product (p) contains the Cu of 19.4at%, the In of 21.72at%, the Ga of 7.28at% and the Se of 51.6at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 4.339wt%.X-ray diffraction (XRD) figure of this black powder [product (p)] is shown in figure 14.
Remove the impurity of product (p)
The quadrol of 105mL is added in the reactive tank, while stir the product (p) that adds 12g again and the Se powder of 0.33g.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 40 hours, so that product (f) is carried out post-processing step.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInGaSe
2Crude product.Clean this CuInGaSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (q)].The composition of this product (q) contains the Cu of 18.42at%, the In of 22.25at%, the Ga of 7.41at% and the Se of 51.92at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.872wt%.X-ray diffraction (XRD) figure of this black powder [product (q)] is shown in figure 15.
The post-processing step of this product (p) makes CuInGaSe
2Carbon content obviously be reduced to 0.872wt% [product (q)] from 4.339wt% [product (p)].
< embodiment 7 (E7) >
Prepare five yuan of Compound C uInGaSeS
Nitrogen-Methylimidazole of 170mL is added in the reactive tank, while stir the InCl that adds 14.6g
3And the GaCl of 1.58g
3While, stir the Na that adds 9.37g more lentamente
2The Na of Se powder and 5.85g
2S obtains first mixture.In second reactive tank, add nitrogen-Methylimidazole of 90mL,, obtain second mixture while stir the CuCl that adds 7.4g again.This first reactant is cooled to 3 ℃, this second reactant is added in this first reactant, and the temperature of reaction is controlled at below 5 ℃ while stir subsequently lentamente.This reaction times continues 12 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain the CuInGaSeS crude product.Clean this CuInGaSeS crude product with solution, this solution contains the ethanol of a large amount of water, 1L and the acetone of 1L, and the CuInGaSeS crude product after then will cleaning carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSeS [product (r)].
The composition of this product (r) contains the Cu of 24.64at%, In, 6.98at%Ga, the Se of 25.88at% and the S of 20.4at% of 22.1at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 2.936wt%.X-ray diffraction (XRD) figure of this black powder [product (r)] is shown in figure 16.
Remove the impurity of product (r)
The quadrol of 90mL is added in the reactive tank, stir the product (r) that adds 10g again and the Se powder of 0.28g on one side, the formation mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.(r) carries out post-processing step to product, makes this mixture continue to carry out back flow reaction 40 hours.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain the CuInGaSeS crude product.Clean this CuInGaSeS crude product with solution, this solution contains the ethanol of a large amount of water, 2L and the acetone of 2L.Make the CuInGaSeS crude product after the cleaning under 150 ℃ of temperature, carry out drying, obtain black powder CuInGaSeS [product (s)].The composition of this product (s) contains the Cu of 24.25at%, the In of 22.1at%, the Ga of 7.11at%, the Se of 26.37at% and the S of 19.38at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.917wt%.X-ray diffraction (XRD) figure of this black powder [product (s)] is shown in figure 17.
The post-processing step of this product (r) makes the carbon content of CuInGaSeS obviously be reduced to 0.917wt% [product (s)] from 2.936wt% [product (r)].
< embodiment 8 (E8) >
Preparation ternary compound CuInSe
2
The quadrol of 150mL is added in the reactive tank,, form mixture while stir the Se powder that adds 2.63g again.Stir this mixture after 5 minutes, while stir the In (NO that adds 10.05g
3)
3, the mixture in this reactive tank is stirred after 15 minutes, while stir the Cu (NO that adds 6.9g again
3)
2Mixture in this reactive tank was stirred after 10 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 45 hours, after reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 1L and the acetone of 1L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (t)].The composition of this product (t) contains the Cu of 25.72at%, the In of 26.83at% and the Se of 47.45at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 3.255wt%.X-ray diffraction (XRD) figure of this black powder [product (t)] is shown in figure 18.
Remove the impurity of product (t)
The quadrol of 80mL is added in the reactive tank, stir the product (t) that adds 10g again and the Se powder of 0.28g on one side, the formation mixture.Mixture in this reactive tank was stirred after 3 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 45 hours, so that product (t) is carried out post-processing step.After aftertreatment is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 1L and the acetone of 1L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (u)].The composition of this product (u) contains the Cu of 25.64at%, the In of 26.72at% and the Se of 47.64at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.912wt%.X-ray diffraction (XRD) figure of this black powder [product (u)] is shown in figure 19.
< comparative example 1 (CE1) >
Preparation ternary compound CuInSe
2
The quadrol of 700mL is added in the reactive tank, while stir the Cu that adds 12g again
2The In of Se and 27.2g
2Se
3And the Se powder of 2.38g forms mixture.Wait to stir this mixture after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 55 hours, after reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2The red fine-powder that crude product and output are more relatively.This redness fine-powder has relative smaller particle size, and therefore being difficult for separating with the mode of filtering this mixture should the redness fine-powder.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 1L and the acetone of 1L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (v)].(composition v) contains the Cu of 24.48at%, the In of 26.8at% and the Se of 48.72at% to this product.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 2.239wt%.X-ray diffraction (XRD) figure of this black powder [product (v)] is shown in figure 20.
< comparative example 2 (CE2) >
Preparation ternary compound CuInSe
2
The quadrol of 600mL is added in the reactive tank, while stir the Se powder that adds 46.3g again, wait to stir 5 minutes after, while stir the InCl that adds 76.24g
34H
2O is to form mixture.Mixture in this reactive tank is stirred after 20 minutes, while stir the CuCl that adds 22.64g again.After waiting to stir 20 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 50 hours, after reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2The red fine-powder that crude product and output are more relatively.This redness fine-powder has relative smaller particle size, and therefore being difficult for separating with the mode of filtering this mixture should the redness fine-powder.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 1L and the acetone of 1L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (w)].The composition of this product (w) contains the Cu of 24.37at%, the In of 28.19at% and the Se of 47.44at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 8.526wt%.X-ray diffraction (XRD) figure of this black powder [product (w)] is shown in figure 21.
< comparative example 3 (CE3) >
Skip test: the CuInSe that does not use the Se powder
2Processing
The quadrol of 130mL is added in the reactive tank, while stir the CuInSe that adds 20g again
2(carbon impurity content is 8.526wt%) is to form mixture.Mixture in this reactive tank was stirred after 5 minutes, continue to stir and be heated to boiling point.Make this mixture continue to carry out back flow reaction 55 hours, after reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain CuInSe
2Crude product.Clean this CuInSe with solution
2Crude product, this solution contain the ethanol of a large amount of water, 1L and the acetone of 1L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (x)].The composition of this product (x) contains the Cu of 26.71at%, the In of 25.59at% and the Se of 47.7at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 2.012wt%.X-ray diffraction (XRD) figure of this black powder [product (x)] is shown in figure 22.
Comparative example 1 and embodiment 1 different be in, comparative example 1 is at Cu
2Se and In
2Se
3Also added the Se powder in the formed reaction mixture.The result shows, the black powder CuInSe that comparative example 1 is produced
2[product (v)], its carbon content be than wanting high without the product (c) of aftertreatment among the embodiment 1, significantly is higher than among the embodiment 1 product (d) through aftertreatment again; It is thus clear that in reaction mixture the Se powder of extra adding, and can't reach the effect that the carbon content that aftertreatment produced of embodiment 1 reduces.
Comparative example 2 and embodiment 4 different be in, comparative example 2 is at Cu
2Se and In
2Se
3The Se powder that adds more amount in the formed reaction mixture.The result shows, the black powder CuInSe that comparative example 2 is produced
2[product (w)], its carbon content without the product (l) of aftertreatment, but significantly is higher than among the embodiment 4 product (m) through aftertreatment in the embodiment 4; It is thus clear that in reaction mixture, add the Se powder of more amount, and can't reach effect like the carbon content that aftertreatment the produced reduction of embodiment 4.
Comparative example 3 and previous embodiment 1 and embodiment 4 different be in, comparative example 3 is carrying out CuInSe
2Aftertreatment the time, do not use the Se powder.The result shows, the black powder CuInSe that comparative example 3 is produced
2After aftertreatment, its carbon content increases before than aftertreatment [product (x)], the visible post-processing step that does not use the Se powder, and can't reduce the content of carbon impurity.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (13)
1. the method for manufacture of a chalcopyrite type cpd is characterized in that it comprises following steps:
Make reaction mixture in first solvent, carry out back flow reaction;
Reacted reaction mixture is filtered and obtain the chalcopyrite type cpd crude product;
This crude product, second solvent are mixed with material after-treatment and form treating mixt, and this material after-treatment is to be selected from S, Se, Te or aforesaid arbitrary combination; And
This treating mixt is removed at this crude product certainly to allow this crude product to carry out the mode of aftertreatment heated under the reflux conditions of impurity, contain M with generation
1, M
2And the chalcopyrite type cpd of A, M
1Be to be selected from Cu, Au, Ag, Na, Li or K, this M
2Be to be selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg or aforesaid arbitrary combination, and this A is selected from S, Se, Te or aforesaid arbitrary combination.
2. the method for manufacture of chalcopyrite type cpd as claimed in claim 1, it is characterized in that: this first solvent and this second solvent are to be selected from alkylamine, N, nitrogen-methyl Pyrrolidine ketone, Methylimidazole, methyl-sulphoxide, oleyl amine, glycerine or terepthaloyl moietie independently of one another.
3. the method for manufacture of chalcopyrite type cpd as claimed in claim 2, it is characterized in that: this first solvent and this second solvent are to be selected from quadrol or Methylimidazole independently of one another.
4. the method for manufacture of chalcopyrite type cpd as claimed in claim 1; It is characterized in that: this method of manufacture also comprises a cleaning step before forming this treating mixt; This cleaning step is to clean this crude product through the use cleaning solution, and this cleaning solution comprises water, alcohol and acetone.
5. the method for manufacture of chalcopyrite type cpd as claimed in claim 1; It is characterized in that: this method of manufacture also comprises a step; This step is to obtain treated crude product with filtering through the reaction mixture of aftertreatment; Then clean this treated crude product with cleaning solution again, this cleaning solution comprises water, alcohol and acetone.
6. the method for manufacture of chalcopyrite type cpd as claimed in claim 5 is characterized in that: this method of manufacture also comprises the step of cleaning this treated crude product with acid solution.
7. the method for manufacture of chalcopyrite type cpd as claimed in claim 1 is characterized in that:
This reaction mixture comprises at least one first compound and at least one second compound, and this first compound comprises M
1And A
1, this second compound comprises M
2And A
1, this A
1Be to be selected from S, Se, Te, Cl
-, Br
-, I
-, OH
-, NO
3 -, SO
4 2-, CH
3COO
-, methyl ethyl diketone acid ion or S, Se and Te arbitrary combination; And
A when this first compound and this second compound
1Be to be selected from Cl
-, Br
-, I
-, OH
-, NO
3 -, SO
4 2-, CH
3COO
-Or during the methyl ethyl diketone acid ion, this reaction mixture also comprises powder, and this powder is to be selected from S, Se, Te or aforesaid arbitrary combination.
8. the method for manufacture of chalcopyrite type cpd as claimed in claim 7, it is characterized in that: this reaction mixture comprises Cu
2Se and In
2Se
3
9. the method for manufacture of chalcopyrite type cpd as claimed in claim 7, it is characterized in that: this reaction mixture comprises Cu
2Se, In
2Se
3And Ga
2Se
3
10. the method for manufacture of chalcopyrite type cpd as claimed in claim 7, it is characterized in that: this reaction mixture comprises Cu
2Se, In
2S
3And Ga
2Se
3
11. the method for manufacture of chalcopyrite type cpd as claimed in claim 7 is characterized in that: this reaction mixture comprises Se, InCl
34H
2O and CuCl.
12. the method for manufacture of chalcopyrite type cpd as claimed in claim 7 is characterized in that: this reaction mixture comprises InCl
3, Na
2Se and CuCl.
13. the method for manufacture of chalcopyrite type cpd as claimed in claim 7 is characterized in that: this reaction mixture comprises InCl
3, GaCl
3, Na
2Se and CuCl.
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Cited By (1)
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| CN111807333A (en) * | 2020-07-28 | 2020-10-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
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Application publication date: 20120829 |