CN102649542A - Production method of chalcopyrite type compound - Google Patents
Production method of chalcopyrite type compound Download PDFInfo
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- CN102649542A CN102649542A CN2011100460340A CN201110046034A CN102649542A CN 102649542 A CN102649542 A CN 102649542A CN 2011100460340 A CN2011100460340 A CN 2011100460340A CN 201110046034 A CN201110046034 A CN 201110046034A CN 102649542 A CN102649542 A CN 102649542A
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Abstract
The invention relates to a production method of a chalcopyrite type compound, which comprises the following steps: reaction mixture is added into a solvent for backflow reaction, so as to generate a chalcopyrite type compound; the reaction mixture comprises at least one first compound and at least one second compound, the first compound comprises M1 and A, the second compound comprises M2 and A, the M1 is selected from Cu, Au, Ag, Na and Li or K, or the M2 is selected from In, Ga, A1, Ti, Zn, Cd, Sn and Mg or a combination of In, Ga, A1, Ti, Zn, Cd, Sn and Mg, and the A is selected from S, Se, Te or a combination of S, Se and Te . The method overcomes the defect of high content of carbon impurities.
Description
Technical field
The present invention relates to a kind of method of manufacture of chalcopyrite type cpd.
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.
People such as Bin Li are at Adv.Mater., and 1999,11, No.17,1456-1459 disclose one and have made CuInSe
2How molten heat (solvothermal) compound method of rice 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 technology 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 technology comprises order and has molecular formula M
3The compound of X with have a molecular formula M
2M
1A
2Compound in ligand solvent, react, to form a kind of molecular formula M that has
3M
1A
2Chalcopyrite type cpd, X can be halogen atom, M
2Can be Li
+, Na
+, K
+Deng.Ternary compound M of above-mentioned arts demand as parent material
2M
1A
2, and compared to binary compound, this ternary compound is more complicated.In addition, prepared chalcopyrite type cpd also has quite high impurity content.Experiment shows that the carbon impurity content of this chalcopyrite type cpd is 4.3wt%.
Announce the 7th, 591 about USP, all disclosures of No. 990 will be incorporated among the present invention as a reference.
This shows that above-mentioned prior art 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 does not see always that for a long time suitable design is developed completion, and 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
Main purpose of the present invention is, overcomes the defective that existing method exists, and a kind of method of manufacture of new chalcopyrite type cpd is provided, and technical problem to be solved is to make it overcome the high defective of carbon impurity content.
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 makes reaction mixture in solvent, carry out back flow reaction, to generate chalcopyrite type cpd; This reaction mixture comprises at least one first compound and at least one second compound, and this first compound comprises M
1And A, this second compound comprises M
2And A, this 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 an aforesaid combination, and this A is selected from S, Se, Te or an aforesaid combination.
The object of the invention and solve its technical problem and also can adopt following technical measures further to realize.
The method of manufacture of aforesaid chalcopyrite type cpd, this method of manufacture also comprise the step of this second compound of the preparation before this reaction mixture carries out back flow reaction, and this step is with containing M
2Chemical substance and powder in solvent solution, carry out back flow reaction, this powder is to be selected from S, Se, Te or an aforesaid combination.
The method of manufacture of aforesaid chalcopyrite type cpd, this solvent solution is made up of water and solvent.
The method of manufacture of aforesaid chalcopyrite type cpd, this solvent are to be selected from alkylamine, N, nitrogen-methyl Pyrrolidine ketone, methyl-sulphoxide, oleyl amine, glycerine or terepthaloyl moietie.
The method of manufacture of aforesaid chalcopyrite type cpd, this solvent is a quadrol.
The method of manufacture of aforesaid chalcopyrite type cpd, this method of manufacture also comprise the step after a reaction in the step of this second compound of preparation is accomplished, and this step is to make this contain M
2Chemical substance and this powder carry out reacted reaction mixture and filter, obtaining crude product, and this crude product is cleaned.
The method of manufacture of aforesaid chalcopyrite type cpd, the cleaning of this crude product are to accomplish through the use cleaning solution, and this cleaning solution comprises water, alcohol and acetone.
The method of manufacture of aforesaid chalcopyrite type cpd, the cleaning of this crude product are through using acid solution to accomplish.
The method of manufacture of aforesaid chalcopyrite type cpd, this method of manufacture also comprise a step after the reaction of this reaction mixture is accomplished, and this step is this reaction mixture is filtered and to obtain crude product, then cleans this crude product with acid solution again.
The method of manufacture of aforesaid chalcopyrite type cpd, this method of manufacture also comprise the step of this first compound of the preparation before this reaction mixture carries out back flow reaction, and this step is with by containing M
1Chemical substance and powder in this solvent, carry out back flow reaction, this powder is to be selected from S, Se, Te or an aforesaid combination.
The method of manufacture of aforesaid chalcopyrite type cpd, this method of manufacture also comprise the step after a reaction in the step of this first compound of preparation is accomplished, and this step is to make to contain M
1Chemical substance and this powder carry out reacted reaction mixture and filter and obtain crude product, and this crude product is cleaned.
The method of manufacture of aforesaid chalcopyrite type cpd; This method of manufacture also comprises the step after a back flow reaction in this reaction mixture is accomplished; This step is that the reaction mixture that this first compound and this second compound are reacted filters, to obtain the chalcopyrite type cpd crude product; This chalcopyrite type cpd crude product, this solvent are mixed with the aftertreatment powder and form mixture; And making this mixture be able to allow this mixture to carry out the mode of aftertreatment under the reflux conditions of this crude product removal impurity, heat, this aftertreatment powder is to be selected from S, Se, Te or an aforesaid combination.
The method of manufacture of aforesaid chalcopyrite type cpd, this reaction mixture comprise Cu-Se first compound and In-Se second compound.
The method of manufacture of aforesaid chalcopyrite type cpd, this reaction mixture comprise Cu-Se first compound, In-Se second compound and Ga-Se second compound.
The method of manufacture of aforesaid chalcopyrite type cpd, this reaction mixture comprise Cu-Se first compound, In-S second compound and Ga-Se second compound.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, the present invention has advantage and beneficial effect at least: this method can overcome the high defective of carbon impurity content.
In sum, the method for manufacture of chalcopyrite type cpd of the present invention makes reaction mixture in solvent, carry out back flow reaction, and to generate chalcopyrite type cpd, this method can overcome the high defective of carbon impurity content.The present invention has obvious improvement technically, has tangible good effect, really is a new and innovative, progressive, practical new design.
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, illustrative embodiment 1 prepared product (c);
Fig. 2 is the X ray diffraction chart, illustrative embodiment 2 prepared products (d);
Fig. 3 is the X ray diffraction chart, illustrative embodiment 3 prepared products (e);
Fig. 4 is the X ray diffraction chart, illustrative embodiment 4 prepared products (g);
Fig. 5 is the X ray diffraction chart, illustrative embodiment 5 prepared products (i);
Fig. 6 is the X ray diffraction chart, illustrative embodiment 6 prepared products (j);
Fig. 7 is the X ray diffraction chart, illustrative embodiment 7 prepared products (k);
Fig. 8 is the X ray diffraction chart, illustrative embodiment 8 prepared products (l);
Fig. 9 is the X ray diffraction chart, illustrative embodiment 9 prepared products (m);
Figure 10 is the X ray diffraction chart, illustrative embodiment 10 prepared products (n);
Figure 11 is the X ray diffraction chart, illustrative embodiment 11 prepared products (o);
Figure 12 is the X ray diffraction chart, illustrative embodiment 12 prepared products (p);
Figure 13 is the X ray diffraction chart, and the existing prepared product of method (CEl) of comparative example 1 utilization is described;
Figure 14 is the X ray diffraction chart, explains that comparative example 2 uses USPs to announce the 7th, 591, No. 990 prepared products of disclosed existing method (CE2);
Figure 15 is the X ray diffraction chart, explains that comparative example 3 uses USPs to announce the 7th, 591, No. 990 prepared products of disclosed existing method (CE3);
Figure 16 is the X ray diffraction chart, explains that comparative example 4 uses USPs to announce the 7th, 591, No. 990 prepared products of disclosed existing method (CE4).
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.
The preferred embodiment of the method for manufacture of chalcopyrite type cpd of the present invention comprises and makes reaction mixture in solvent, carry out back flow reaction, to generate chalcopyrite type cpd.This reaction mixture comprises at least one first compound and at least one second compound.This first compound is for comprising M
1And any compound of A, this second compound is for comprising M
2And any compound of A.This 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 an aforesaid combination, and this A is selected from S, Se, Te or an aforesaid combination.
Be applicable to solvent of the present invention for example alkylamine, N (DMF), nitrogen-methyl Pyrrolidine ketone (NMP), methyl-sulphoxide (DMSO), oleyl amine, glycerine or terepthaloyl moietie etc.Preferably, this solvent is an alkylamine.More preferably, this solvent is a quadrol.
In preferred embodiment of the present invention; This method of manufacture also comprises the step after a back flow reaction in this reaction mixture is accomplished; This step is to make this first compound and this second compound carry out reacted reaction mixture to filter; To obtain the chalcopyrite type cpd crude product, then clean this crude product with cleaning solution, this cleaning solution comprises water, alcohol and acetone.
Preferably, this method of manufacture also comprises a post-processing step, and it is after cleaning with this cleaning solution, forms mixture through this chalcopyrite type cpd crude product, this solvent are mixed with the aftertreatment powder; And making this mixture be able to allow this mixture to carry out the mode of aftertreatment under the reflux conditions of this crude product removal impurity, heat, this aftertreatment powder is to be selected from S, Se, Te or an aforesaid combination.Can to carry out the used solvent of back flow reaction with above-mentioned this reaction mixture be identical to the example of used solvent in this post-processing step.
Preferably, this method of manufacture also comprises a step, and this step is to use acid solution to clean this chalcopyrite type cpd crude product, then utilizes this cleaning solution to carry out the second time again and cleans.
Preferably, this second compound is obtained through following steps: will contain M
2The chemical substance and the powder that reach X carry out back flow reaction in solvent solution, to obtain reaction mixture.This X representes a negatively charged ion, and this negatively charged ion is to be selected from halide anions, nitrate ion (NO
3 -) or sulfate ion (SO
4 2-), this powder is to be selected from S, Se, Te or an aforesaid combination; After above-mentioned reaction is accomplished, this reaction mixture is filtered, to obtain the second compound crude product; Use cleaning solution to clean this second compound crude product, this cleaning solution comprises water, alcohol and acetone; And make this crude product carry out drying.Preferably, this solvent solution is solvent or is made up of water and solvent.It is identical that the example of solvent as used herein can carry out the used solvent of back flow reaction with above-mentioned reaction mixture.
Preferably; This method of manufacture also is included in the step of using after this cleaning solution carries out cleaning for the first time to this second compound crude product; This step is to use acid solution to clean this crude product, carries out cleaning the second time also dry this crude product with this cleaning solution more subsequently.
Preferably, this first compound is obtained through following steps: with M
1X chemical substance and powder carry out back flow reaction in solvent solution, to obtain reaction mixture, this X representes a negatively charged ion, and this negatively charged ion is to be selected from halide anions, nitrate ion (NO
3 -) or sulfate ion (SO
4 2-), this powder is to be selected from S, Se, Te or an aforesaid combination; After this reaction is accomplished, this reaction mixture is filtered, to obtain the first compound crude product; Use cleaning solution to clean this first compound crude product, this cleaning solution comprises water, alcohol and acetone; And make this crude product carry out drying.Preferably, this solvent solution is solvent or is made up of water and solvent.It is identical that the example of solvent as used herein can carry out the used solvent of back flow reaction with above-mentioned this reaction mixture.
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%.
Announce the 7th, 591 compared to USP, No. 990 disclosed methods, the total overall reaction thing that method of manufacture of the present invention is used, just first compound and second compound all contain among S, Se and the Te at least one of them; And USP is announced the 7th, 591, No. 990 and is only used selenate (selenide) as reactant.Above-mentioned difference makes the carbon content of the prepared chalcopyrite type cpd of the present invention be lower than USP and announces the 7th, 591, the carbon content of No. 990 prepared compounds of method.
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(M
2A)
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, 4L and the acetone of 4L.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 (M
1A)
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(M
1M
2A)
The quadrol of 9000mL is added in the reactive tank, stirs the product (a) that adds 600g again and product (b) the formation mixture of 260g on one side, wait to stir this mixture after 5 minutes, lasting stirring also is 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 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 25.43at%, 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.
< embodiment 2 (E2) >
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 20g 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 a 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 (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.
Post-processing step among the embodiment 2 makes CuInSe
2Carbon content obviously be reduced to 0.877wt% [product (d)] from 1.536wt% [product (c)].
< embodiment 3 (E3) >
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 the cooling of this mixture, 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 4 (E4) >
The cleanup acid treatment of product (a)
5% nitric acid of 6500mL is added in the reactive tank,, form mixture while stir the product (a) that adds 780g again.With this mixture heating up to 45 ℃ also lasting stirring 4 hours.After finishing dealing with and treating the cooling of this mixture, 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 Vandyke brown powder In
2Se
3[product (f)].The composition of this product (f) contains the In of 42.32at% and the Se of 57.68at%.This Vandyke brown powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.692wt%.
Preparation ternary Compound C uInSe
2(M
1M
2A)
The quadrol of 7500mL is added in the reactive tank, stirs the product (f) that adds 600g again and the product (b) of 278.2g on one side, the formation mixture waited to stir this mixture after 5 minutes, and lasting stirring also is 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 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 (g)].The composition of this product (g) contains the Cu of 24.78at%, the In of 24.47at% and the Se of 47.75at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.612wt%.X-ray diffraction (XRD) figure of this black powder [product (g)] is as shown in Figure 4.
Embodiment 4 and embodiment 1 different are in, the product of embodiment 4 (a) (In
2Se
3) before mixing with product (b) and reacting, also comprise one and use the acid solution processed steps.The result shows product In
2Se
3Carbon impurity content be reduced to 0.692wt% [product (f)], product C uInSe significantly by 4.81wt% [product (a)]
2Carbon impurity content be reduced to 0.612wt% [product (g)] by 1.536wt% [product (c)].
< embodiment 5 (E5) >
Preparation InSe (M
2A)
The water of 1400mL is added in the reactive tank, while stir the InCl that adds 470.4g
34H
2O, be stirred to dissolving after, while stir the quadrol that adds 7000mL lentamente again in this reactive tank (because this mixing process is thermopositive reaction, therefore add the mode of speed with the control quadrol, the temperature maintenance that makes this mixture is below 70 ℃).Be not more than 40 ℃ mode with the temperature of keeping this mixture, while stir add 188.2g again the Se powder to this reactive tank, 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 30 hours.After reaction is accomplished and treated this mixture cooling, filter this mixture, to obtain the InSe crude product.Clean this InSe crude product with solution, this solution contains the ethanol of a large amount of water, 2L and the acetone of 2L.Make the InSe crude product after the cleaning under 150 ℃ of temperature, carry out drying, obtain tawny powder InSe [product (h)].The composition of this product (h) contains the In of 47.48at% and the Se of 52.25at%.This tawny powder is carried out ultimate analysis, show the carbon impurity that wherein contains 3.432wt%.
Preparation ternary compound CuInSe
2(M
1M
2A)
The quadrol of 9000mL is added in the reactive tank, stirs the product (h) that adds 600g again and the product (b) of 280g on one side, form a mixture, wait to stir this mixture after 5 minutes, lasting stirring also is heated to boiling point.Make this mixture continue to carry out back flow reaction 40 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 (i)].The composition of this product (i) contains the Cu of 26.86at%, the In of 26.79at% and the Se of 46.35at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 1.013wt%.X-ray diffraction (XRD) figure of this black powder [product (i)] is as shown in Figure 5.
Embodiment 5 and embodiment 1 different are in, the InCl of embodiment 5
34H
2O and Se powder form product InSe through reaction under the environment of the mixed solution of water and quadrol, and 1 of embodiment reacts and formation product In under the environment that quadrol is only arranged
2Se
3The result shows that the carbon impurity content of product InSe is reduced to 3.432wt% [product (h)] by 4.821wt% [product (a)]; Product C uInSe
2Carbon impurity content be reduced to 1.013wt% [product (i)] by 1.536wt% [product (c)].
< embodiment 6 (E6) >
Remove the impurity of product (i)
The quadrol of 6000mL is added in the reactive tank, stir the product (i) that adds 730g again and the Se powder of 20g 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 (c) is carried out a 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 (j)].The composition of this product (j) contains the Cu of 26.16at%, the In of 26.58at% and the Se of 47.26at%.This black powder is carried out ultimate analysis, show the carbon impurity that wherein contains 0.579wt%.X-ray diffraction (XRD) figure of this black powder [product (j)] is as shown in Figure 6.
< embodiment 7 (E7) >
Preparation quaternary compound CuInGaSe
2(M
1M
2M
3A)
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 (k)].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%.X-ray diffraction (XRD) figure of this black powder [product (k)] is as shown in Figure 7.
< embodiment 8 (E8) >
Remove the impurity of product (k)
The quadrol of 120mL is added in the reactive tank, stir the product (k) 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 40 hours, so that product (k) is carried out a 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 (l)].The composition of this product (l) 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 (l)] is as shown in Figure 8.
< embodiment 9 (E9) >
Remove the impurity of product (l)
5% nitric acid of 85mL is added in the reactive tank,, form mixture while stir the product (l) that adds 10g again.With this mixture heating up to 45 ℃ also lasting stirring 4 hours.After finishing dealing with and treating the cooling of this mixture, 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 (m)].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 (m)] is as shown in Figure 9.
< embodiment 10 (E7) >
Prepare five yuan of Compound C uInGaSeS (M
1M
2M
3A
1A
2)
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 (n)].The composition of this product (n) 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 (n)] is shown in figure 10.
< embodiment 11 (E11) >
Remove the impurity of product (n)
The quadrol of 120mL is added in the reactive tank, stir the product (n) that adds 13g 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 40 hours, so that product (n) is carried out a 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 (o)].The composition of this product (o) 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 (o)] is shown in figure 11.
< embodiment 12 (E12) >
Remove the impurity of product (o)
5% nitric acid of 100mL is added in the reactive tank,, form mixture while stir the product (o) that adds 12g again.With this mixture heating up to 45 ℃ also lasting stirring 4 hours.After finishing dealing with and treating the cooling of this mixture, 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 (p)].The composition of this product (p) 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 (p)] is shown in figure 12.
< comparative example 1 (CE1) >
Preparation ternary compound CuInSe
2(M
1M
2A)
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 lentamente
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, 4L and the acetone of 4L.Make the CuInSe after the cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (CE1)].The composition of this product (CE1) 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 that the carbon impurity that wherein contains 9.216wt% does.X-ray diffraction (XRD) figure of this black powder [product (CE1)] is shown in figure 13.
< comparative example 2 (CE2) >
Preparation ternary compound CuInSe
2(M
1M
2A)
The compound of comparative example 2 is to announce the 7th, 591 according to USP, and No. 990 disclosed method is prepared from.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, filters 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, 4L and the acetone of 4L, the CuInSe after then will cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInSe
2[product (CE2)].
The composition of this product (CE2) contains the Cu of 26.02at%, 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 (CE2)] is shown in figure 14.
< comparative example 3 (CE3) >
Preparation quaternary compound CuInGaSe
2(M
1M
2M
3A)
The compound of comparative example 3 is to announce the 7th, 591 according to USP, and No. 990 disclosed method is prepared from.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 a solution
2Crude product, this solution contain the ethanol of a large amount of water, 4L and the acetone of 4L, the CuInGaSe after then will cleaning
2Crude product carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSe
2[product (CE3)].
The composition of this product (CE3) contains the Se of In, 7.28at% and 51.6wt% of Cu, the 21.72at% of 19.4at%.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 (CE3)] is shown in figure 15.
< comparative example 4 (CE4) >
Prepare five yuan of Compound C uInGaSeS (M
1M
2M
3A
1A
2)
The compound of comparative example 4 is to announce the 7th, 591 according to USP, and No. 990 disclosed method is prepared from.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, 4L and the acetone of 4L, and the CuInGaSeS crude product after then will cleaning carries out drying under 150 ℃ of temperature, obtain black powder CuInGaSeS [product (CE4)].
The composition of this product (CE4) 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 (CE4)] is shown in figure 16.
Table 1
| Product | Classes of compounds | Carbon content (wt%) | |
| Embodiment 1 | ?(c) | Ternary | 1.536 |
| Comparative example 1 | ?(CE1) | Ternary | 9.216 |
| Comparative example 2 | ?(CE2) | Ternary | 4.322 |
| Embodiment 7 | ?(k) | Quaternary | 1.332 |
| Comparative example 3 | ?(CE3) | Quaternary | 4.339 |
| Embodiment 10 | ?(n) | Five yuan | 0.928 |
| Comparative example 4 | ?(CE4) | Five yuan | 2.936 |
Table 1 shows that respectively the carbon content of the ternary brass ore deposit type compound of embodiment 1, comparative example 1 and comparative example 2 compares; The carbon content of the quaternary chalcopyrite type cpd of embodiment 7 and comparative example 3 relatively; And the carbon content of five yuan of chalcopyrite type cpds of embodiment 10 and comparative example 4 relatively.The result shows that by the prepared chalcopyrite type cpd of method provided by the present invention, its carbon content obviously reduces with the compound of existing method preparation.
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 (15)
1. the method for manufacture of a chalcopyrite type cpd is characterized in that:
Make reaction mixture in solvent, carry out back flow reaction, to generate chalcopyrite type cpd;
This reaction mixture comprises at least one first compound and at least one second compound, and this first compound comprises M
1And A, this second compound comprises M
2And A, this 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 an aforesaid combination, and this A is selected from S, Se, Te or an aforesaid combination.
2. the method for manufacture of chalcopyrite type cpd as claimed in claim 1, it is characterized in that: this method of manufacture also comprises the step of this second compound of the preparation before this reaction mixture carries out back flow reaction, and this step is with containing M
2Chemical substance and powder in solvent solution, carry out back flow reaction, this powder is to be selected from S, Se, Te or an aforesaid combination.
3. the method for manufacture of chalcopyrite type cpd as claimed in claim 2, it is characterized in that: this solvent solution is made up of water and solvent.
4. the method for manufacture of chalcopyrite type cpd as claimed in claim 3, it is characterized in that: this solvent is to be selected from alkylamine, N, nitrogen-methyl Pyrrolidine ketone, methyl-sulphoxide, oleyl amine, glycerine or terepthaloyl moietie.
5. the method for manufacture of chalcopyrite type cpd as claimed in claim 4, it is characterized in that: this solvent is a quadrol.
6. the method for manufacture of chalcopyrite type cpd as claimed in claim 2 is characterized in that: this method of manufacture also comprises the step after a reaction in the step of this second compound of preparation is accomplished, and this step is to make this contain M
2Chemical substance and this powder carry out reacted reaction mixture and filter, obtaining crude product, and this crude product is cleaned.
7. the method for manufacture of chalcopyrite type cpd as claimed in claim 6 is characterized in that: the cleaning of this crude product is through using cleaning solution to accomplish, and this cleaning solution comprises water, alcohol and acetone.
8. the method for manufacture of chalcopyrite type cpd as claimed in claim 6 is characterized in that: the cleaning of this crude product is through using acid solution to accomplish.
9. the method for manufacture of chalcopyrite type cpd as claimed in claim 1; It is characterized in that: this method of manufacture also comprises the step after a reaction in this reaction mixture is accomplished; This step is this reaction mixture is filtered and to obtain crude product, then cleans this crude product with acid solution again.
10. the method for manufacture of chalcopyrite type cpd as claimed in claim 1, it is characterized in that: this method of manufacture also comprises the step of this first compound of the preparation before this reaction mixture carries out back flow reaction, and this step is with by containing M
1Chemical substance and powder in this solvent, carry out back flow reaction, this powder is to be selected from S, Se, Te or an aforesaid combination.
11. the method for manufacture of chalcopyrite type cpd as claimed in claim 10 is characterized in that: this method of manufacture also comprises the step after a reaction in the step of this first compound of preparation is accomplished, and this step is to make to contain M
1Chemical substance and this powder carry out reacted reaction mixture and filter and obtain crude product, and this crude product is cleaned.
12. the method for manufacture of chalcopyrite type cpd as claimed in claim 1; It is characterized in that: this method of manufacture also comprises the step after a back flow reaction in this reaction mixture is accomplished; This step is that the reaction mixture that this first compound and this second compound are reacted filters, to obtain the chalcopyrite type cpd crude product; This chalcopyrite type cpd crude product, this solvent are mixed with the aftertreatment powder and form mixture; And making this mixture be able to allow this mixture to carry out the mode of aftertreatment under the reflux conditions of this crude product removal impurity, heat, this aftertreatment powder is to be selected from S, Se, Te or an aforesaid combination.
13. the method for manufacture of chalcopyrite type cpd as claimed in claim 1 is characterized in that: this reaction mixture comprises Cu-Se first compound and In-Se second compound.
14. the method for manufacture of chalcopyrite type cpd as claimed in claim 1 is characterized in that: this reaction mixture comprises Cu-Se first compound, In-Se second compound and Ga-Se second compound.
15. the method for manufacture of chalcopyrite type cpd as claimed in claim 1 is characterized in that: this reaction mixture comprises Cu-Se first compound, In-S second compound and Ga-Se second compound.
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| CN104591262A (en) * | 2015-01-26 | 2015-05-06 | 河南科技大学 | Method for preparing mercury sulfide nanoparticles through dripping reflux |
| CN109879306A (en) * | 2019-03-26 | 2019-06-14 | 湖北大学 | (CuIn)xZn2(1-x)S2Nano particle and its preparation method and application |
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