CN102432057A - Method for preparing cuprous oxide-indium trioxide solid solution superfine powder - Google Patents
Method for preparing cuprous oxide-indium trioxide solid solution superfine powder Download PDFInfo
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- CN102432057A CN102432057A CN2011102948344A CN201110294834A CN102432057A CN 102432057 A CN102432057 A CN 102432057A CN 2011102948344 A CN2011102948344 A CN 2011102948344A CN 201110294834 A CN201110294834 A CN 201110294834A CN 102432057 A CN102432057 A CN 102432057A
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- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 36
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title abstract 4
- 239000006104 solid solution Substances 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 11
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 10
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 10
- VPJDHCVPTOMIRT-UHFFFAOYSA-N indium(3+) oxocopper oxygen(2-) Chemical compound [Cu]=O.[O-2].[In+3].[O-2].[O-2].[In+3] VPJDHCVPTOMIRT-UHFFFAOYSA-N 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000003483 aging Methods 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000000975 co-precipitation Methods 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RLWNPPOLRLYUAH-UHFFFAOYSA-N [O-2].[In+3].[Cu+2] Chemical compound [O-2].[In+3].[Cu+2] RLWNPPOLRLYUAH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 copper halide Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing cuprous oxide-indium trioxide solid solution superfine powder. The method comprises the following steps of: performing ultrasonic chemical reduction coprecipitation reaction on 9.99 to 99.99 percent of metal indium (In), copper sulfate (CuSO4.5H2O) and concentrated sulfuric acid (H2SO4) which serve as raw materials by using a sodium hydroxide (NaOH) solution as a precipitating agent, a glucose (C6H12O12) solution as a reducing agent and absolute ethanol (CH3CH2OH) as a stabilizing agent and a dispersing agent; reducing and aging at constant temperature; performing centrifugal separation; washing, and dispersing; and drying, calcining, and thus obtaining the cuprous oxide-indium trioxide solid solution superfine powder. The obtained cuprous oxide-indium trioxide solid solution superfine powder has the particle size of 30 to 50nm, has spherical particles, high purity and a high dispersing property and is distributed uniformly; and the method is simple, has a short production period and is convenient to operate.
Description
Technical field
The present invention relates to the preparation method of a kind of Red copper oxide-indium trioxide sosoloid ultrafine powder, belong to powder metallurgical technology.
Background technology
Copper indium oxide (copper Indium oxide, CuInO
2Abbreviation CIO) belongs to yellow copper structure p type transparent conductive material.The transparent conductive material visible light transmissivity of CIO preparation is more than 80%, and energy gap is 3.9eV.CIO doping Ca
2+Or Sn
4+After can be made into p type or n type all considerable the passing through conductive film, turn to voltage of electric conductivity and Seebeck coefficient be all very excellent components and parts of photoelectric characteristics such as p-n homojunction of 1.8V.CIO can be used as fields such as electrophotographic recording, fixedly demonstration, optical memory, distinction display apparatus, anti-electrostatic (electrostatic shielding), electrooptical device, heat reflection, big area heating element, aerospace, photoelectrochemistry, variable color are luminous, air-sensitive detection, superconduction, daily use chemicals, is hyundai electronics and photovoltaic industry important functional material.
At present, the method for preparing superfine powder both at home and abroad is many, mainly contains solid phase method, liquid phase method and vapor phase process three major types, and wherein solid phase method is divided into solid reaction process, alloying, positively charged ion cross reaction method etc.; And liquid phase method is divided into the chemical reaction precipitator method, parallel-flow precipitation method, chemical coprecipitation, sol-gel processing, microemulsion method, hydrothermal synthesis method etc.; The gas phase rule is divided into methods such as inert-gas condensation method, laser ablation method, energising heating vaporization, sputtering method, plasma body gas-phase chemical reaction method (PCVD) method, chemical gas phase coacervation, spray heating decomposition and vacuum vapor deposition method, and wherein liquid phase method is used the most extensive and ripe.
Bipolarity transparent conductive material copper indium oxide (CuInO
2) preparation of superfine powder, present known main preparation methods has solid reaction process, positively charged ion cross reaction method and chemical coprecipitation.There has been a large amount of solid reaction processes that facts have proved to be difficult to; Even possibly not be prepared into the CIO superfine powder; Hahn (Zeitschrift fuer Anorganische Chemie.1955; 279:281-288), Wofgang (Silikattechnik. 1970,21:45-46), Makhova (Phys. State. Sol.. 2006,203:2861-2866), Shimode (J. Solid State Chem. 2000; 151:15-20), (Densed Matter:2004 16:S811-S816) waits the people once to attempt with Cu to Garlea
2O and In
2O
3Or In (OH)
3Be raw material, adopt solid reaction process to prepare CuInO
2Powder, but all end in failure.Positively charged ion cross reaction method is to study at most, and development is relatively ripe, prepares the method for CIO superfine powder.Shimode (J. Solid State Chem. 2000,151:15-20), Garlea (Densed Matter:2004,16 (11): S811-S816), Yanagi (Mat. Res. Soc. Symp. Proc.. 2001; 666:F3.14/1-F3.14/6), Shimode (Materials Transactions. 2000,41:1111-1113), Park (J. Solid State Chem. 2003,173:335-358), Li (J. Solid State Chem.. 2005; 178:285-294), Teplin (Applied Physics Letter. 2004; 85 (10): 3789-3791), Yanagi (Applied Physics Letters, 2001,78 (11): 1583-1585), Sasaki (Journal of Physics and Chemistry of Solids. 2003; 64 (9-10): 1675-1679) wait the people to adopt positively charged ion cross reaction method to be prepared into the CIO superfine powder respectively; But long flow path, raw material monovalence copper halide is prone to oxidized, volatile; Need in closed environment; Insulation reaches 144h under 350 ℃, and consuming time of a specified duration, reaction efficiency is low; The impurity that exists in the reaction product is difficult to Ex-all, for the inaccessible requirement of the high target of purity requirement.
Chemical coprecipitation belongs to liquid phase method; Be meant and select one or more soluble metallic salts, be made into solution, make each element be the lewis' acid attitude and exist in solution by certain metering ratio; Through adding suitable precipitation agent; Make desired substance almost at one time in deposition, crystallization fully equably, prepare the method for superfine powder through processes such as dehydrations, heat treated, be a kind of noticeable method.Song Ning (Chinese invention patent in 2007,200710066492.4) uses chemical coprecipitation to be prepared into the copper indium oxide superfine powder that particle diameter is 20～40nm.This method is simple because of technology, and is with short production cycle, easy to operate, low for equipment requirements, less investment, production cost is lower, be suitable for scale operation and be widely used, but this method system be equipped with presoma CuO and In (OH)
3When mixed powder is calcined, must make Cu
+ 2Become Cu
+ 1The difficulty of compound is very high, and powder is prone to reunite (being that superfine powder is agglomerated into larger particles again).
Summary of the invention
The object of the present invention is to provide that a kind of method is simple, with short production cycle, easy to operate, Cu
+ 2Be prone to become Cu
+ 1The method for preparing Red copper oxide-indium trioxide sosoloid ultrafine powder of compound, this method gained Red copper oxide-indium trioxide sosoloid ultrafine powder can be used for preparing CuInO
2Target, low for equipment requirements, less investment, production cost be low, be suitable for scale operation, realizes through following technical proposal.
The preparation method of a kind of Red copper oxide-indium trioxide sosoloid ultrafine powder, following each step of process:
A. getting purity and be 99.9～99.99% indium metal, to join mass percentage concentration be in 98% the sulfuric acid; Be warming up to 60～80 ℃ again; And continue stirring until indium metal and dissolve fully, add entry after being cooled to room temperature then, making concentration is the indium sulfate solution of 100～200g/L;
B. get copper sulfate and be added to the water, and continue stirring until copper sulfate and dissolve fully, make the copper-bath that concentration is 100～200g/L;
C. after steps A gained indium sulfate solution and step B gained copper-bath being mixed; Leave standstill 3～5min; Place 30～60 ℃ of following UW waters bath with thermostatic control to stir again; Simultaneously with the speed of 5～10mL/min add concentration be 150～250g/L sodium hydroxide solution to pH be 9.5～11.5, and then be 2 ︰ 1.1～1.2 by the mol ratio of mixing solutions and glucose solution, adding concentration is that the glucose solution of 280～420g/L reduces ageing 25～45min; Speed spinning with 5000rpm goes out throw out and repetitive scrubbing then, up to detecting no SO with barium chloride solution
4 2-Till, use absolute ethanol washing again 1～3 time, obtain very high Red copper oxide of uniformity coefficient and indium hydroxide mixed powder;
D. step C gained mixed powder is placed 80～100 ℃ of following microwave drying 3～7min, again that mixed powder is levigate, and place under vacuum or the condition of nitrogen gas with 800～1100 ℃ of microwave calcinations, be incubated 5～20min again, make Cu
2O-In
2O
3The sosoloid ultrafine powder.
Water among said steps A and the B is ultrapure water.
Copper sulfate among the said step B is analytically pure copper sulfate.
The present invention is with 9.99～99.99% indium metal (In), copper sulfate (CuSO
45H
2O), the vitriol oil (H
2SO
4) be raw material, be precipitation agent with sodium hydroxide (NaOH) solution, glucose (C
6H
12O
12) solution is reductive agent, absolute ethyl alcohol (CH
3CH
2OH) be stablizer and dispersion agent,, finally make Red copper oxide-indium trioxide sosoloid ultrafine powder through sonochemistry reduction coprecipitation reaction, constant temperature reduction ageing, spinning, washing dispersion, drying and calcining.The particle diameter of gained Red copper oxide-indium trioxide sosoloid ultrafine powder is 30～50nm, and it is spherical that powder granule is, and product purity is high, is evenly distributed good dispersivity.
Compare with known technology, the present invention has following advantage and positively effect:
(1) adopts sonochemistry reduction co-precipitation-microwave drying calcining to unite and prepare Cu
2O-In
2O
3The sosoloid ultrafine powder, technology such as integrated ultrasonic, chemical reduction co-precipitation, microwave have been strengthened chemical reduction coprecipitation reaction process, and each sub-Technology is organically combined, the good product quality of preparing is easy to realize suitability for industrialized production;
(2) in the reduction ageing process, make the CuO powder be reduced into Cu
2The O powder when having overcome chemical coprecipitation and preparing the CIO powder, adopts the method for control calcination atmosphere, avoids Cu
+ 2Change Cu into
+ 1The control difficulty is big during compound;
(3) overcome positively charged ion cross reaction method long flow path, consuming time for a long time, low, the complex process of efficient, the product purity shortcoming that is difficult to improve;
(4) avoid solid reaction process and prepared metastable state Cu InO
2The difficulty of powder, product can be directly as preparation CuInO
2The raw material of target;
(5) adopt stable dispersant absolute ethanol washing presoma, utilize hyperacoustic dissemination, the agglomeration traits of powder is effectively solved, and makes the temperature of reaction of chemical reduction co-precipitation remove reduction, has shortened the reaction times, has shortened Cu
2O-In
2O
3The preparation cycle of sosoloid ultrafine powder;
(6) adopt modernized microwave drying calcining powder technology, make loose, the easy mill of product structure, particle is thin, has accelerated drying and calcining speed greatly, and the whole production cycle obviously shortens, and has reduced energy consumption.
Embodiment
To combine embodiment further to illustrate content of the present invention below, but these instances do not limit protection scope of the present invention.
Embodiment 1
A. getting purity and be 99.99% indium metal, to join mass percentage concentration be in 98% the sulfuric acid, to be warming up to 65 ℃ again, and continue stirring until indium metal and dissolve fully, adds ultrapure water after being cooled to room temperature then, and making concentration is the indium sulfate solution of 100g/L;
B. get copper sulfate and join in the ultrapure water, and continue stirring until copper sulfate and dissolve fully, make the copper-bath that concentration is 100～200g/L;
C. after steps A gained indium sulfate solution and step B income analysis bright sulfur acid copper solutions being mixed; Leave standstill 3min; Place 40 ℃ of following UW waters bath with thermostatic control to stir again; Simultaneously with the speed of 5mL/min add concentration be 200g/L sodium hydroxide solution to pH be 10, and then be 2 ︰ 1.1 by the mol ratio of mixing solutions and glucose solution, adding concentration is that the glucose solution of 360g/L reduces ageing 25min; Speed spinning with 5000rpm goes out throw out and repetitive scrubbing then, up to detecting no SO with barium chloride solution
4 2-Till, use absolute ethanol washing again 2 times, obtain very high Red copper oxide of uniformity coefficient and indium hydroxide mixed powder;
D. step C gained mixed powder is placed 80 ℃ of following microwave drying 3min, again that mixed powder is levigate, and place under vacuum or the condition of nitrogen gas with 950 ℃ of microwave calcinations, be incubated 7min again, make the Cu that mean particle size is 26.79nm
2O-In
2O
3The sosoloid ultrafine powder.
Embodiment 2
A. getting purity and be 99.93% indium metal, to join mass percentage concentration be in 98% the sulfuric acid, to be warming up to 80 ℃ again, and continue stirring until indium metal and dissolve fully, adds ultrapure water after being cooled to room temperature then, and making concentration is the indium sulfate solution of 150g/L;
B. get copper sulfate and join in the ultrapure water, and continue stirring until copper sulfate and dissolve fully, make the copper-bath that concentration is 150g/L;
C. after steps A gained indium sulfate solution and step B income analysis bright sulfur acid copper solutions being mixed; Leave standstill 4min; Place 60 ℃ of following UW waters bath with thermostatic control to stir again; Simultaneously with the speed of 8mL/min add concentration be 150g/L sodium hydroxide solution to pH be 9.5, and then be 2 ︰ 1.2 by the mol ratio of mixing solutions and glucose solution, adding concentration is that the glucose solution of 280g/L reduces ageing 35min; Speed spinning with 5000rpm goes out throw out and repetitive scrubbing then, up to detecting no SO with barium chloride solution
4 2-Till, use absolute ethanol washing again 1 time, obtain very high Red copper oxide of uniformity coefficient and indium hydroxide mixed powder;
D. step C gained mixed powder is placed 90 ℃ of following microwave drying 5min, again that mixed powder is levigate, and place under vacuum or the condition of nitrogen gas with 800 ℃ of microwave calcinations, be incubated 5min again, make the Cu that median size is 27.54nm
2O-In
2O
3The sosoloid ultrafine powder.
Embodiment 3
A. getting purity and be 99.9% indium metal, to join mass percentage concentration be in 98% the sulfuric acid, to be warming up to 60 ℃ again, and continue stirring until indium metal and dissolve fully, adds ultrapure water after being cooled to room temperature then, and making concentration is the indium sulfate solution of 200g/L;
B. get copper sulfate and join in the ultrapure water, and continue stirring until copper sulfate and dissolve fully, make the copper-bath that concentration is 200g/L;
C. after steps A gained indium sulfate solution and step B income analysis bright sulfur acid copper solutions being mixed; Leave standstill 5min; Place 30 ℃ of following UW waters bath with thermostatic control to stir again; Simultaneously with the speed of 10mL/min add concentration be 250g/L sodium hydroxide solution to pH be 11.5, and then be 2 ︰ 1.1 by the mol ratio of mixing solutions and glucose solution, adding concentration is that the glucose solution of 420g/L reduces ageing 45min; Speed spinning with 5000rpm goes out throw out and repetitive scrubbing then, up to detecting no SO with barium chloride solution
4 2-Till, use absolute ethanol washing again 3 times, obtain very high Red copper oxide of uniformity coefficient and indium hydroxide mixed powder;
D. step C gained mixed powder is placed 100 ℃ of following microwave drying 7min, again that mixed powder is levigate, and place under vacuum or the condition of nitrogen gas with 1100 ℃ of microwave calcinations, be incubated 20min again, make the Cu that median size is 27.12nm
2O-In
2O
3The sosoloid ultrafine powder.
Claims (3)
1. the preparation method of Red copper oxide-indium trioxide sosoloid ultrafine powder is characterized in that through following each step:
A. getting purity and be 99.9～99.99% indium metal, to join mass percentage concentration be in 98% the sulfuric acid; Be warming up to 60～80 ℃ again; And continue stirring until indium metal and dissolve fully, add entry after being cooled to room temperature then, making concentration is the indium sulfate solution of 100～200g/L;
B. get copper sulfate and be added to the water, and continue stirring until copper sulfate and dissolve fully, make the copper-bath that concentration is 100～200g/L;
C. after steps A gained indium sulfate solution and step B gained copper-bath being mixed; Leave standstill 3～5min; Place 30～60 ℃ of following UW waters bath with thermostatic control to stir again; Simultaneously with the speed of 5～10mL/min add concentration be 150～250g/L sodium hydroxide solution to pH be 9.5～11.5, and then be 2 ︰ 1.1～1.2 by the mol ratio of mixing solutions and glucose solution, adding concentration is that the glucose solution of 280～420g/L reduces ageing 25～45min; Speed spinning with 5000rpm goes out throw out and repetitive scrubbing then, up to detecting no SO with barium chloride solution
4 2-Till, use absolute ethanol washing again 1～3 time, obtain Red copper oxide and indium hydroxide mixed powder;
D. step C gained mixed powder is placed 80～100 ℃ of following microwave drying 3～7min, again that mixed powder is levigate, and place under vacuum or the condition of nitrogen gas with 800～1100 ℃ of microwave calcinations, be incubated 5～20min again, make Cu
2O-In
2O
3The sosoloid ultrafine powder.
2. preparation method according to claim 1 is characterized in that: the water among said steps A and the B is ultrapure water.
3. preparation method according to claim 1 and 2 is characterized in that: the copper sulfate among the said step B is analytically pure copper sulfate.
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Cited By (4)
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| US10059852B2 (en) | 2013-04-02 | 2018-08-28 | Shenzhen Byd Auto R&D Company Limited | Metal compound, method for preparing the same, selective metallization of surface of substrate with the metal compound |
| CN109980107A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | CuMO2And preparation method thereof, luminescent device |
| CN111632587A (en) * | 2019-03-01 | 2020-09-08 | 天津大学 | Indium-indium trioxide heterogeneous nano material composite electrocatalyst and preparation method and application thereof |
| CN114232003A (en) * | 2021-12-16 | 2022-03-25 | 西北师范大学 | Cu preparation by utilizing cathode glow discharge electrolytic plasma technology2Method for producing O nanoparticles |
Citations (2)
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|---|---|---|---|---|
| CN1539740A (en) * | 2003-04-22 | 2004-10-27 | 中南大学 | Method for preparing composite material of Nano crystal between copper oxide and indium oxide |
| CN101214994A (en) * | 2007-12-27 | 2008-07-09 | 昆明理工大学 | Process for preparing nano powder of copper indium oxide |
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|---|---|---|---|---|
| CN1539740A (en) * | 2003-04-22 | 2004-10-27 | 中南大学 | Method for preparing composite material of Nano crystal between copper oxide and indium oxide |
| CN101214994A (en) * | 2007-12-27 | 2008-07-09 | 昆明理工大学 | Process for preparing nano powder of copper indium oxide |
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| 曹艳: "葡萄糖还原法制备氧化亚铜的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 7 December 2009 (2009-12-07), pages 28 - 39 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10059852B2 (en) | 2013-04-02 | 2018-08-28 | Shenzhen Byd Auto R&D Company Limited | Metal compound, method for preparing the same, selective metallization of surface of substrate with the metal compound |
| CN109980107A (en) * | 2017-12-28 | 2019-07-05 | Tcl集团股份有限公司 | CuMO2And preparation method thereof, luminescent device |
| CN109980107B (en) * | 2017-12-28 | 2020-12-01 | Tcl科技集团股份有限公司 | CuMO2Preparation method thereof and light-emitting device |
| CN111632587A (en) * | 2019-03-01 | 2020-09-08 | 天津大学 | Indium-indium trioxide heterogeneous nano material composite electrocatalyst and preparation method and application thereof |
| CN111632587B (en) * | 2019-03-01 | 2022-09-09 | 天津大学 | Indium-indium trioxide heterogeneous nano material composite electrocatalyst and preparation method and application thereof |
| CN114232003A (en) * | 2021-12-16 | 2022-03-25 | 西北师范大学 | Cu preparation by utilizing cathode glow discharge electrolytic plasma technology2Method for producing O nanoparticles |
| CN114232003B (en) * | 2021-12-16 | 2023-09-12 | 西北师范大学 | Cu preparation by utilizing cathode glow discharge electrolysis plasma technology 2 Method of O nanoparticles |
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