CN101407328B - Method for preparing zinc aluminum oxide nano-powder - Google Patents
Method for preparing zinc aluminum oxide nano-powder Download PDFInfo
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- CN101407328B CN101407328B CN2008102334482A CN200810233448A CN101407328B CN 101407328 B CN101407328 B CN 101407328B CN 2008102334482 A CN2008102334482 A CN 2008102334482A CN 200810233448 A CN200810233448 A CN 200810233448A CN 101407328 B CN101407328 B CN 101407328B
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- 238000000034 method Methods 0.000 title claims abstract description 25
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000011858 nanopowder Substances 0.000 title claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 17
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 7
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 229940037003 alum Drugs 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 12
- 238000000975 co-precipitation Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 1
- 239000001164 aluminium sulphate Substances 0.000 abstract 1
- 235000011128 aluminium sulphate Nutrition 0.000 abstract 1
- 239000001099 ammonium carbonate Substances 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 239000012024 dehydrating agents Substances 0.000 abstract 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WDYMMLFNWBOKFO-UHFFFAOYSA-L aluminum;zinc;sulfate Chemical compound [Al+3].[Zn+2].[O-]S([O-])(=O)=O WDYMMLFNWBOKFO-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- ZPUBJHQABOZYOK-UHFFFAOYSA-L aluminum zinc carbonate Chemical compound C([O-])([O-])=O.[Zn+2].[Al+3] ZPUBJHQABOZYOK-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- 239000012530 fluid Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing zinc-aluminium oxide (ZAO) nanometer powder, which takes zinc sulfate and aluminium sulphate as materials, ammonia, sodium hydroxide and ammonium carbonate as precipitators, absolute ethyl alcohol as a stabilizing agent and a dehydrating agent, and deionized water as a solvent, and carries out ultrasonic chemistry coprecipitation reaction at the temperature of 30-60 DEG C, and then carries out temperature-preservation ageing, centrifuge separating, washing, microwave drying and sintering to prepare the ZAO nanometer powder. The method utilizes ultrasonic cavitation reaction environment for controlling the conglobation of the ZAO nanometer powder, thus leading the coprecipitation reaction temperature to be lowered down and shortening the preparation period of the ZAO nanometer powder. The prepared ZAO nanometer powder has particle size of 15-30nm, specific surface area of 40-75m<2>/g, spherical particles, high product purity, even distribution, and good dispersion and photoelectric properties.
Description
One, technical field: the present invention relates to a kind of method for preparing zinc aluminum oxide nano-powder, belong to powder metallurgical technology.
Two, background technology
(Zinc Aluminum Oxide is ZnAl to Zinc-aluminium
2O
4Be called for short ZAO) be a kind of n type transparent conductive oxide material, because of having big carrier concentration and optical energy gap, and show good photoelectric characteristic, it is the base mateiral of modern optical electronic industry, more because the used starting material zinc-aluminium of ZAO film aboundresources, with low cost, nontoxic, thermostability and good chemical stability, being considered to has one of transparent conductive material of development potentiality at present most, be applied to solar cell, liquid-crystal display is in anti-electrostatic specific function window coating and other photoelectric device fields.
At present, the method for preparing nano-powder both at home and abroad is a lot, mainly contains homogeneous coprecipitation method, aqueous solution coprecipitation method, electrolytic process, sol-gel processing, spray heating decomposition and mechanical milling method etc.In these methods, liquid phase method is that industrial preparation ultrafine powder is most widely used, its basic skills is to select one or more soluble metallic salts, press composition metering wiring solution-forming, make each element be the lewis' acid attitude, use a kind of precipitation agent again, with the desired substance precipitation from homogeneous solution, crystallize out, make ultrafine powder through process such as dehydration or heating.And the chemistry of aqueous solution coprecipitation method is noticeable a kind of method, this method adopts and adds precipitation agent from the outside, its technology is simple, the cycle short, easy to operate, less demanding to equipment, less investment, production cost is low, be suitable for scale operation and be widely adopted, but this method exists outstanding agglomeration in concrete preparation process, promptly nanoparticle is agglomerated into bigger particle again.For the preparation of n type transparent conductive material zinc aluminum oxide nano-powder, present known main preparation methods has homogeneous coprecipitation method, aqueous solution coprecipitation method, solid reaction process and sol-gel processing etc.(chemistry and biotechnology .2006,23 (9): such as Xu Li 15-17.) with Zn (Ac)
2.2H
2O, Al (NO
3)
39H
2O, citric acid and ethanol etc. are raw material, and adopting sol-gel method to prepare median size is the linen nanometer ZAO composite granule of 22nm.(JournalofUniversity of Science and Technology Beijing, 2006,13 (4): such as Wei Shao 346-349.) with Al (NO
3)
39H
2O, Zn (NO
3)
26H
2O and NH
4HCO
3Be raw material, adopting chemical coprecipitation to prepare median size at 800 ℃ of calcining 1.5h is that 21.3nm, specific surface area are 3.62m
2The ZAO nano-powder of/g.(Xi'an Institute of Technology's journal such as Liu Xiulan.2006,26 (1): be raw material with zinc acetate, aluminum nitrate, lanthanum nitrate hexahydrate, polyoxyethylene glycol, ammoniacal liquor and ethanol etc. 60-63.), the median size that adopts co-precipitation-supercritical fluid drying preparation to mix lanthanum is the ZAO nano-powder of 20nm.There is the Heating temperature height in these methods, and soaking time is long, and technological process is amplified difficult, and the energy consumption height needs to add practical problemss such as organic reagent.
Three, summary of the invention
The object of the present invention is to provide a kind of method for preparing zinc aluminum oxide nano-powder.With zinc sulfate (ZnSO
47H
2O), Tai-Ace S 150 (Al
2(SO
4)
318H
2O) be raw material, with ammoniacal liquor, sodium hydroxide (NaOH), volatile salt (NH
4)
2CO
3Be precipitation agent, with dehydrated alcohol (CH
3CH
2OH) be stablizer and dewatering agent, deionized water is a solvent, carries out the sonochemistry coprecipitation reaction under 30-60 ℃ temperature, the insulation ageing, and centrifugation, again through washing, microwave drying and calcining, the preparation zinc aluminum oxide nano-powder.Prepared zinc aluminum oxide nano-powder particle diameter is 15-30nm, and specific surface area is 40-75m
2/ g, powder granule are spherical, and the product purity height is evenly distributed, and dispersiveness and photoelectric properties are good.
The present invention finishes according to the following steps.
1) gets zinc sulfate and Tai-Ace S 150 and add deionized water respectively, be warming up to 30-55 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make zinc sulfate and aluminum sulfate aqueous solution;
2) aqueous solution of gained is diluted to contains Zn
2+0.5-2.0mol/L solution of zinc sulfate and concentration be the alum liquor of 0.1-1.0mol/L, again two kinds of solution are pressed ZnO: Al
2O
3=95-97: the preparation of 3-5 weight percent mixes, the two stirring and evenly mixing 3-5min is placed in the ultrasonic water bath with thermostatic control and stirs, controlled temperature 30-60 ℃, simultaneously, successively dripping the NaOH solution of concentration 0.5-2.0mol/L and ammonia soln or concentration that concentration is 2.0-6.0mol/L is the (NH of 0.5-2.0mol/L
4)
2CO
3Solution to pH value is 8-11, and reaction aging 30-60min is then with centrifugation of 3000-4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L
2There is not SO in the solution check washings
4 2-Till, will precipitate and use absolute ethanol washing 2-3 time, the precipitation that obtains is the Zinc-aluminium presoma;
3) the Zinc-aluminium presoma is put into the microwave oven drying, controlled temperature is 80-100 ℃, time 3-5min, and taking-up is finely ground to below the 30nm, places microwave oven to calcine again, and controlled temperature is 250-900 ℃, time 5-15min.Make zinc aluminum oxide nano-powder.
Compare advantage and positively effect that the present invention has with known technology
1) adopt sonochemistry co-precipitation-microwave drying calcining integrated process to prepare the ZAO nano-powder, strengthen co-precipitation chemical reaction or transmittance process by the effective integration of technology such as ultrasonic wave, microwave, one Technology is organically combined, the good product quality that makes is easy to realize suitability for industrialized production;
2) need not to add organic reagent and dispersion agent, utilize ultrasonic wave to have the reaction environment that ultrasonic cavitation produces, control the reunion of ZAO nano-powder, the coprecipitation reaction temperature is reduced, the reaction times shortens.Shortened the preparation cycle of ZAO nano-powder;
3) loose, the easy mill of powder structure is calcined in microwave drying, particle is little, rate of heating is fast.
Four, description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Five, embodiment
Embodiment 1: get zinc sulfate and Tai-Ace S 150 and add deionized water respectively, be warming up to 45 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make the zinc-aluminium sulfate solution; Zinc sulfate solution is diluted to contains Zn
2+2.0mol/L solution to get 600ml and concentration be that the alum liquor 59ml of 0.5mol/L mixes, the two stirring and evenly mixing 3min is placed on 50kHz, stir in the ultrasonic water bath with thermostatic control of 100W, 50 ℃ of controlled temperature, NaOH solution to the pH value that drips concentration simultaneously and be 2.0mol/L is 9, is cooled to 35 ℃ and then drips (the NH that concentration is 2.0mol/L again
4)
2CO
3Solution to pH value is 10 to end, and ageing 30min is then with centrifugation of 4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L
2There is not SO in the solution check washings
4 2-Till, to precipitate with absolute ethanol washing and precipitate 3 times, obtain basic carbonate zinc-aluminium presoma, presoma is put into the dry 5min of microwave oven (microwave power 750W, frequency 2450MHz), controlled temperature is 85 ℃, take out fine grinding, place microwave oven to calcine again, microwave power is 700W, and temperature is 500 ℃, time 13min makes product ZAO nano-powder.Its median size is 20nm, specific surface area 56.76m
2It is spherical that/g, powder granule all are, and is evenly distributed not have to reunite good dispersity.Its optical property shows as ultraviolet region (100-400nm) and has the intensive absorptivity, and visible region (400-800nm) has high perviousness, and infrared region (800-3500nm) has high reflectivity, and electric property shows as has low resistivity.
Embodiment 2: get zinc sulfate (ZnSO
47H
2O) and Tai-Ace S 150 (Al
2(SO
4)
318H
2O) add deionized water respectively, be warming up to 45 ℃, continue stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, make the zinc-aluminium sulfate solution; Zinc sulfate solution is diluted to contains Zn
2+1.0mol/L dilute solution to get 1200ml and concentration be that the alum liquor 59ml of 0.5mol/L mixes, the two stirring and evenly mixing 3min is placed on 50kHz, stir in the ultrasonic water bath with thermostatic control of 100W, 55 ℃ of controlled temperature, NaOH solution to the pH value that drips concentration simultaneously and be 2.0mol/L is 9.5, and ammonia soln to the pH value that then drips concentration again and be 5.0mol/L is 10.5 to end ageing 50min, then with centrifugation of 3000r/min speed and repetitive scrubbing precipitation, up to BaCl with 0.2mol/L
2There is not SO in the solution check washings
4 2-Till, to precipitate with absolute ethanol washing and precipitate 3 times, obtain zinc-aluminium oxyhydroxide presoma, presoma is put into the dry 3min of microwave oven (microwave power 750W, frequency 2450MHz), controlled temperature is 100 ℃, take out fine grinding, place microwave oven to calcine again, microwave power is 700W, and temperature is 550 ℃, time 10min makes product ZAO nano-powder.Its median size is 15nm, specific surface area 74.37m
2It is spherical that/g, powder granule all are, and is evenly distributed not have to reunite good dispersity.Its optical property shows as ultraviolet region (100-400nm) and has the intensive absorptivity, and visible region (400-800nm) has high perviousness, and infrared region (800-3500nm) has high reflectivity, and electric property shows as has low resistivity.
Claims (1)
1. a method for preparing zinc aluminum oxide nano-powder is got zinc sulfate and Tai-Ace S 150 and is added deionized water respectively, is warming up to 30-55 ℃, continues stirring until zinc sulfate and Tai-Ace S 150 dissolves fully, makes zinc sulfate and aluminum sulfate aqueous solution respectively; With the aqueous solution dilution of gained, again two kinds of solution are prepared mixing by weight percentage, the two stirring and evenly mixing is placed in the ultrasonic water bath with thermostatic control and stirs, and simultaneously, successively drips NaOH solution and ammonia soln or (NH
4)
2CO
3Solution to pH value is 8-11, and behind the reaction aging, centrifugation and repetitive scrubbing precipitation do not have SO in washings
4 2-Till, will precipitate and use absolute ethanol washing, the precipitation that obtains is the Zinc-aluminium presoma, and it is dry that the Zinc-aluminium presoma is put into microwave oven, and calcining makes zinc aluminum oxide nano-powder, it is characterized in that:
The dilution of described zinc sulfate and aluminum sulfate aqueous solution is it to be diluted to contain Zn
2+0.5-2.0mol/L solution of zinc sulfate and concentration be the alum liquor of 0.1-1.0mol/L;
The weight percent of described two kinds of solution is ZnO: Al
2O
3=95-97: 3-5, the two stirring and evenly mixing 3-5min is placed in the ultrasonic water bath with thermostatic control and stirs, and controlled temperature 30-60 ℃, ammonia soln or concentration that the NaOH solution of dropping concentration 0.5-2.0mol/L and concentration are 2.0-6.0mol/L are the (NH of 0.5-2.0mol/L
4)
2CO
3Solution to pH value is 8-11, and reaction aging 30-60min is then with centrifugation of 3000-4000r/min speed and repetitive scrubbing precipitation, up to the BaCl with 0.2mol/L
2There is not SO in the solution check washings
4 2-Till, will precipitate and use absolute ethanol washing 2-3 time, the precipitation that obtains is the Zinc-aluminium presoma;
The drying of presoma is that controlled temperature is 80-100 ℃ in the described microwave oven, time 3-5min, and taking-up is finely ground to below the 30nm; Calcining is that controlled temperature is 250-900 ℃ in the described microwave oven, time 5-15min.
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| CN2008102334482A CN101407328B (en) | 2008-10-16 | 2008-10-16 | Method for preparing zinc aluminum oxide nano-powder |
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| CN101407328B true CN101407328B (en) | 2011-11-16 |
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| CN101560059B (en) * | 2009-05-27 | 2012-09-12 | 中南大学 | Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof |
| CN103482679A (en) * | 2013-07-17 | 2014-01-01 | 南开大学 | Aluminum zinc oxide (AZO) nano powder and preparation method of AZO sintered bodies |
| CN106315639A (en) * | 2016-08-02 | 2017-01-11 | 上海理工大学 | Ultrasonic preparation method of high-purity ZnAl2O4 nano particles |
| CN107170583A (en) * | 2017-05-15 | 2017-09-15 | 北京化工大学 | A kind of method and its application that the aluminium-doped zinc oxide for dye-sensitized solar cell anode is prepared based on hydrotalcite |
| CN110482592B (en) * | 2019-08-19 | 2022-02-11 | 西北矿冶研究院 | Process for preparing nano zinc oxide from steelmaking ash |
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