CN101559340B - Method for preparing non-agglomerate nanometer material - Google Patents

Method for preparing non-agglomerate nanometer material Download PDF

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CN101559340B
CN101559340B CN2009100669664A CN200910066966A CN101559340B CN 101559340 B CN101559340 B CN 101559340B CN 2009100669664 A CN2009100669664 A CN 2009100669664A CN 200910066966 A CN200910066966 A CN 200910066966A CN 101559340 B CN101559340 B CN 101559340B
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nano material
dispersing agent
polyethylene glycol
nano
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CN101559340A (en
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杨小牛
卢智慧
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a method for preparing a non-agglomerate nanometer material, and solves the problem of agglomeration in preparing the nanometer material through high-temperature calcination. The method concretely comprises that: one or two kinds of salt required by preparing the nanometer material is dissolved in water solution of a macromolecular dispersing agent, and added with a precipitating agent under the conditions of heating and stirring; after the reaction is finished, precursors of the nanometer material are evenly dispersed in an interpenetrating network of the macromoleculardispersing agent, residual ions are removed, and the solution is dried to obtain the even blend of the precursors of the nanometer material and the macromolecular dispersing agent; and the blend is c alcinated in nitrogen, hydrogen, argon, ammonia gas or mixed gas thereof to remove coating matters generated on the surface of the nanometer material after the macromolecular dispersing agent is calcinated at oxygen-free atmosphere so as to obtain the non-agglomerate nanometer material; or the blend is clacinated in a Muffle furnace to directly remove the macromolecular dispersing agent coated on the surface of the nanometer material so as to obtain the non-agglomerate nanometer material. The method is easy and feasible, non-toxic and environment-friendly, and has universality.

Description

A kind of method for preparing non-agglomerate nanometer material
Technical field
The present invention relates to a kind of method for preparing non-agglomerate nanometer material, belong to the inorganic nano material preparing technical field.
Background technology
After nano material and nanometer technology were born and emerge rapidly in late 1980s; Just become in the new material the most dynamicly and, have irreplaceable effect and critical role promoting the national economic development and Future Society progress by the research field of extensive concern.Nano material shows the distinct special performance of many megacryst materials traditional with it because of its small-size effect, skin effect, quantum size effect and macro quanta tunnel effect etc. make it at aspects such as power, heat, sound, magnetic, light, electricity, catalysis, sensitivities; Such as sintering temperature reduction, chemism increase, corrosion resistance enhancing, density reduction, thermal conductivity reduction, elastic modelling quantity reduction, electrical conductivity rising, thermal coefficient of expansion raising or the like; These unique charm can bring glad tidings to fine chemistry industry undoubtedly, make nano material be used as catalyst, lubricant, conductive filler, sensing element, sintering aid, photosensitive material, magnetic material etc.
Up to now, nano material has been widely used in numerous researchs and application, and is still containing huge potential.Yet, because the existence of small size, high surface energy and intergranular gravitation is easy to cause the interparticle reunion of nano material.If under hot environment, prepare; The reunion degree is obviously aggravation especially, even the phenomenon that caking occurs and grow up, and has reduced the active of nano material so that has had a strong impact on its performance; All bring very big inconvenience for simultaneously blend, homogenizing, packing and application, make its development prospect run into bottleneck.More especially the nano material of high-temperature calcination preparation under certain atmosphere, occurred in largely limit its development and the application of reunion, Du Shangfeng etc. utilize co-precipitation-calcination method to prepare Ga-doped zinc oxide conductive powder body (J.Am.Ceram.Soc.2006; 89,2440), its electrical conductivity increases along with the rising of calcining heat; Yet; After temperature was higher than 540 ℃, agglomeration also aggravated along with the rising of temperature, can't obtain nano level conductive powder body.The performance of similar problem such as nano material is optimized along with the rising of calcining heat, but along with the rising of calcining heat, the tendency that nano material is reunited is also more and more serious, its premium properties that should have is declined to a great extent even disappears.If we can solve the agglomeration traits of higher temperature, just can obtain the better nano material of performance.
People are in order to address this problem; Also develop some and prevented the preparation method that nano material is reunited; Chinese patent CN 101028584A discloses a kind of the reunion when preventing the nano material high-temperature calcination and method that particle is grown up; Specifically be that nano-powder with certain grain size is immersed in certain hour in certain density phosphoric acid or the phosphate solution, suction filtration, washing, oven dry then, the gained powder is after 200-800 ℃ of high-temperature calcination; Obtain not having the nano particle of reunion, but this method is introduced the impurity that removes not fall easily in the nanometer lattice.Chinese patent CN1288085C discloses a kind of no-agglomeration nano α-Al 2O 3The preparation method of powder is dispersed in nano carbon black in the aluminum salt solution earlier, adds alkali reaction and ageing then; Behind the filtration washing; Filter cake 1000-1200 ℃ of processing down in inert atmosphere earlier is fired to surperficial coating to eliminate then in 600-800 ℃ air retort, consider that nano carbon black is difficult for being dispersed in the middle of the nano material; Need high-intensity mechanical agitation, this method can receive restriction significantly in commercial production.The king is precious to provide a kind of using uniform precipitation-supercritical carbon dioxide seasoning to prepare nano magnesia with waiting; Specifically be in the aqueous solution, to adopt the Preparation by Uniform Precipitation magnesium hydrate precipitate; Displace the water in the deposition with ethanol, adopt the supercritical carbon dioxide seasoning to remove the ethanol in the deposition again, ethanol is separated out recovery through separator; Carbon dioxide can recycle, and the dried magnesium hydroxide of high-temperature calcination obtains the nanoscale magnesium oxide powder.This method has solved the agglomeration traits when the preparation nano-powder is dry, but complex equipments, and complex steps has strengthened industrialized cost.Chinese patent CN 10033998C provides a kind of polymer protection to prepare the superfine nano method of magnesium oxide, is raw material with magnesium nitrate and hexamethylenetetramine, at organic reagent polyethylene glycol-400 and N; Under the protection of dinethylformamide; Magnesian predecessor is prepared in magnesium nitrate and hexamethylenetetramine reaction, and vacuum constant temperature is dry; Calcining at high temperature makes superfine nano magnesia at last.The acquisition that this method is successful the reunion degree little, the uniform nano magnesia of distribution of particles has enriched the technology of preparing of non-agglomerate nanometer material.Li Qiangs etc. use NH with the basic zinc carbonate deposition 4The aqueous solution of OH washs; Improve the reunion degree (Journal of Inorganic Materials of ZnO powder when the high-temperature calcination through changing its current potential; 1999,14 (5): 813-817), unfortunate this method can only be improved the dispersiveness of powder; Can not solve the agglomeration traits of nano-powder in the hot environment fully, and nano material is not had universal significance.So, develop a kind of simplely, with low cost, and have the method that the solution nano material of general dissemination is reunited in high-temperature calcination, just become the long-awaited thing of people.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of method for preparing non-agglomerate nanometer material, this method is preventing that nano material is of universal significance aspect the reunion in the preparation process of high-temperature calcination.
The step and the condition of preparation non-agglomerate nanometer material are following:
1) macromolecule dispersing agent is dissolved in the water, concentration is 20-2000mg/mL; Described macromolecule dispersing agent is a solid polyethylene glycol; Polyvinyl alcohol; Polyacrylic acid; Carboxymethyl cellulose; Hydroxyethylcellulose; Polyvinylpyrrolidone; HPMA; Maleic acid-acrylic acid copolymer; Acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer; Acrylic acid-hydroxypropyl acrylate copolymer; Acrylic acid-acrylic acid ester-co-polymer of sulfonate; A kind of in acrylic acid-acrylic acid ester-phosphonic acids-sulfonate quadripolymer and the polyoxyethylated alkyl phenol formaldehyde condensation products;
Described solid polyethylene glycol is a kind of in polyethylene glycol-1000, polyethylene glycol-2000, polyethylene glycol-3000, polyethylene glycol-4000, polyethylene glycol-6000, polyethylene glycol-8000, cetomacrogol 1000 0 and the Macrogol 2000 0;
The solution temperature of described polyvinyl alcohol is 100 ℃; The solution temperature of other macromolecule dispersing agents is normal temperature;
2) the following salt that will prepare nano material of normal temperature is dissolved in the above-mentioned solution; Concentration is 10-300mg/mL; Be to stir 0.5-24h under 50-99 ℃ the condition in heating-up temperature; In the process of heated and stirred, add precipitating reagent by the stoichiometric proportion that generates the maximum deposition then, the deposition that obtains the precursor of nano material is dispersed among the solution of macromolecule dispersing agent; The salt of described preparation nano material is one or both in nitrate, sulfate, chlorate, acetate, oxalates, isopropoxide and the tartrate of zinc, aluminium, magnesium, indium, gallium, silicon, zirconium, tin or titanium; Described precipitating reagent is a kind of in NaOH, potassium hydroxide, lithium hydroxide, ammoniacal liquor, hexamethylenetetramine (HMT), urea, sodium acid carbonate, sodium carbonate, ammonium carbonate and the carbonic hydroammonium;
During synthesizing doped type binary composite oxide nano-material, two kinds of salt mol ratios of required preparation nano material are 1: 200-1: 5;
3) with step 2) the macromolecule dispersing agent solution of the presoma of the homodisperse nano material that obtains encloses in the bag filter; In secondary water, soaked 1-5 days; Remove residual ion; Put into drying box then in 60-200 ℃ of oven dry, the time is 10-72h, obtains the dry blends of the presoma and the macromolecule dispersing agent of nano material;
The presoma of the nano material that 4) step 3) is obtained and the dry blends of macromolecule dispersing agent; Under particular atmosphere, calcine 0.5-12h in 200-1300 ℃; Product after the calcining naturally cools to room temperature; Then it is inserted in the Muffle furnace in 300-500 ℃ of calcining 0.5-3h, remove macromolecule dispersing agent through oxygen-free atmosphere calcining back the coating in the nano-material surface generation, obtain not having the nano material of reunion; Described particular atmosphere is one or both in hydrogen, argon gas, ammonia and the nitrogen;
Perhaps, the presoma of the nano material that step 3) is obtained and the dry blends of macromolecule dispersing agent are inserted in the Muffle furnace in 300-1300 ℃ of calcining 0.5-12h, make macromolecule dispersing agent become gas it is directly removed, and obtain not having the nano material of reunion.
Beneficial effect: 1. may be dissolved in the water of non-toxic inexpensive the low and environmental protection of commercial production cost as macromolecule dispersing agent.2. macromolecule dispersing agent is easy to form adsorption layer on the surface of solid particle; The nano particle that in its solution, generates or the precursor of nano particle can form the dispersion of stable homogeneous; After the drying, the precursor of nano particle or nano particle is in the interpenetrating networks of macromolecule dispersing agent, and macromolecule dispersing agent generates amorphous carbon through high-temperature calcination; Or a large amount of gases, can effectively prevent the reunion of nano material.3. in work in the past; People utilize the precipitation method to prepare the precursor of nano material such as the subcarbonate of metal etc., in calcination process, decompose the gas that generates, and are playing certain function aspect the reunion that stops nano material; But; After the precursor decomposition finished, along with the increase of calcination time, nano material still can be reunited.And method provided by the invention because macromolecule dispersing agent generates the existence of amorphous carbon under oxygen-free atmosphere, has effectively stoped the reunion of nano material, and these amorphous carbon can be removed through the following calcining of air at low temperatures; The nano material of high-temperature calcination preparation in air is because the decomposition of macromolecule dispersing agent has effectively stoped the reunion of nano material.4. method of the present invention has universality aspect the non-agglomerate nanometer material utilizing high-temperature calcination to prepare.
Description of drawings
Fig. 1 is the transmission electron microscope light field photo according to the nano zinc oxide powder without coacervation of embodiment 1 said condition preparation.
Fig. 2 is the transmission electron microscope light field photo according to the nano zinc oxide powder without coacervation of embodiment 4 said condition preparations.
Fig. 3 is the transmission electron microscope light field photo according to the no reunion bitter earth nano powder of embodiment 8 said condition preparations.
Fig. 4 is the transmission electron microscope light field photo according to the no reunion bitter earth nano powder of embodiment 11 said condition preparations.
Fig. 5 is the transmission electron microscope light field photo according to the no reunion bitter earth nano powder of embodiment 15 said condition preparations.
Fig. 6 is the transmission electron microscope light field photo according to the no reunion aluminum-doped zinc oxide nanometer powder of embodiment 57 said condition preparations.
The specific embodiment
Embodiment 1: polyethylene glycol-6000 is configured to the aqueous solution that concentration is 100mg/mL; Be dissolved in zinc nitrate in the aqueous solution of polyethylene glycol-6000 then; Concentration is 100mg/mL, adds with six methines, four ammoniums of zinc nitrate equimolar amounts and in 50 ℃ of heated and stirred 2h, is poured in the bag filter; In secondary water, soaked 5 days, remove unnecessary ion.It is dry to put into electric drying oven with forced convection then, and temperature is 80 ℃, and the time is 10h, obtains the dry blends of zinc hydroxide and polyethylene glycol-6000, places 600 ℃ tube type resistance furnace to calcine 2h down in hydrogen atmosphere then, naturally cools to room temperature.Put into Muffle furnace at last in 350 ℃ of calcining 0.5h, remove the coating that polyethylene glycol-6000 generates on the zinc oxide nano-particle surface after the hydrogen atmosphere calcining, obtain not having the zinc oxide nano-particle of reunion.
Step and the condition of embodiment 1-7 are as shown in table 1, and remaining obtains not having the zinc oxide nano-particle of reunion and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion zinc oxide nano-particle of table 1. embodiment 1-7 preparation
Embodiment 1 2 3 4 5 6 7
Condition 1 100 20 500 200 1500 1800 2000
Condition 2 a5 b f g e m c
Condition 3 100 150 10 220 250 270 300
Condition 4 Nitrate Sulfate Chlorate Acetate Oxalates Tartrate Nitrate
Condition 5 1∶1 1∶2 1∶2 1∶2 1∶1 1∶2 1∶2
Condition 6 HMT Ammoniacal liquor LiOH KOH Na 2CO 3 Urea NaOH
Condition 7 50 60 70 80 99 55 65
Condition 8 2 12 15 5 24 18 20
Condition 9 5 4 3 2 1 5 5
Condition 10 80 90 100 120 160 200 180
Condition 11 10 72 48 20 30 40 60
Condition 12 600 700 800 500 400 300 200
Condition 13 2 1.5 0.5 3 12 6 8
Condition 14 H A Y N 5H∶2Y 1N∶9H H
Condition 15 350 300 400 420 350 320 450
Condition 16 0.5 3 1 2 2.5 1.5 0.8
Note: the practical implementation condition of condition 1-16 representative is:
Condition 1: the concentration of macromolecule dispersing agent, unit: mg/mL;
Condition 2: macromolecule dispersing agent; A1-a8, b, c, d, e, f, g, h, i, j, k, l, the used macromolecule dispersing agent of m representative: a1 represents polyethylene glycol-1000; A2 represents polyethylene glycol-2000, and a3 represents polyethylene glycol-3000, and a4 represents polyethylene glycol-4000; A5 represents polyethylene glycol-6000; A6 represents polyethylene glycol-8000, and a7 represents cetomacrogol 1000 0, and a8 represents Macrogol 2000 0; B represents polyvinyl alcohol; C represents polyacrylic acid; D represents carboxymethyl cellulose; E represents hydroxyethylcellulose; The f polyvinylpyrrolidone; G represents HPMA; H represents maleic acid-acrylic acid copolymer; I represents acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer; J represents acrylic acid-hydroxypropyl acrylate copolymer; K represents acrylic acid-acrylic acid ester-co-polymer of sulfonate; L represents acrylic acid-acrylic acid ester-phosphonic acids-sulfonate quadripolymer; M represents the polyoxyethylated alkyl phenol formaldehyde condensation products;
The concentration of the precursor used salt of condition 3. preparation nano materials, unit: mg/mL; If the salt of preparation nano material has two kinds, then is the total concentration of two kinds of salt;
The kind of the salt of the precursor of condition 4. preparation nano materials;
The stoichiometric proportion of condition 5. salt and precipitating reagent;
Condition 6: the kind of used precipitating reagent;
Condition 7: the heated and stirred temperature, unit: ℃;
Condition 8: heated and stirred time, unit: h;
Condition 9: the time that the precursor of macromolecule dispersing agent and nano material soaks in bag filter, unit: day
Condition 10: the temperature that blend is dried in drying box, unit: ℃;
Condition 11: the time that blend is dried in drying box, unit: h
Condition 12: the temperature of calcining in the tube type resistance furnace, unit: ℃;
Condition 13: the time of calcining in the tube type resistance furnace, unit: h;
Condition 14: calcination atmosphere: H represents hydrogen, and N represents nitrogen, and Y represents argon gas, and A represents ammonia, and K represents air, the volume ratio of two kinds of gases of digitized representation of H, N, Y, A, K front.Represent like: 9H: 1N that the volume ratio of hydrogen and nitrogen is 9: 1 in the calcination atmosphere.
Condition 15: the temperature of calcining in the Muffle furnace, unit: ℃;
Condition 16: the time of calcining in the Muffle furnace, unit: h;
"/" expression in the form is omitted this step and is not promptly experienced this implementation condition.
Above note, below all embodiment with.
Embodiment 8: polyethylene glycol-8000 is dissolved in the water, obtains the solution that concentration is 100mg/mL, be dissolved in magnesium nitrate in the solution of polyethylene glycol-8000 then; Concentration is 200mg/mL, adds NaOH then, and magnesium nitrate and NaOH mol ratio are 1: 2; And heated and stirred, temperature is 90 ℃, the time is 3h; Be poured into then in the bag filter, in secondary water, soaked 5 days, remove unnecessary ion.It is dry to put into electric drying oven with forced convection, and temperature is 90 ℃, and the time is 12h, obtains the dry blends of magnesium hydroxide and polyethylene glycol-8000, places 800 ℃ tube type resistance furnace to calcine 2h down in nitrogen atmosphere then, naturally cools to room temperature.Put into Muffle furnace at last in 400 ℃ of calcining 2.5h, remove the polyethylene glycol-8000 that is coated on the bitter earth nano particle surface, obtain not having the bitter earth nano particle of reunion.
Step and the condition of embodiment 8-14 are as shown in table 2, and remaining obtains not having reunion bitter earth nano particle at last with embodiment 1.
The step and the condition of the no reunion bitter earth nano particle of table 2. embodiment 8-14 preparation
Embodiment 8 9 10 11 12 13 14
Condition 1 100 20 300 500 1000 1500 2000
Condition 2 a6 b m a2 1 c e
Condition 3 200 50 100 150 30 10 300
Condition 4 Nitrate Sulfate Chlorate Sulfate Acetate Nitrate Chlorate
Condition 5 1∶2 1∶1 1∶2 1∶1 1∶2 1∶2 1∶2
Condition 6 NaOH HMT LiOH Na 2CO 3 NaHCO 3 KOH Urea
Condition 7 90 50 70 60 80 99 75
Condition 8 3 12 24 0.5 20 10 15
Condition 9 5 2 3 4 1 5 5
Condition 10 90 150 60 200 120 180 80
Condition 11 12 30 48 72 20 40 10
Condition 12 800 500 600 700 800 / 1300
Condition 13 2 3 5 4 1 / 1.5
Condition 14 N N N N Y K Y
Condition 15 400 550 600 1000 1300 700 800
Condition 16 2.5 3 1.2 0.8 0.5 2.2 1
The step condition of embodiment 15-21 is as shown in table 3, and remaining obtains not having reunion aluminium oxide nano particle and being uniformly dispersed with embodiment 1 at last.
Table 3 is the step and the condition of the no reunion aluminium oxide nano particle of embodiment 15-21 preparation
Embodiment 15 16 17 18 19 20 21
Condition 1 200 20 1200 100 1500 180 2000
Condition 2 g i l a8 e m f
Condition 3 100 10 300 85 25 150 120
Condition 4 Chlorate Nitrate Sulfate Isopropoxide Chlorate Nitrate Sulfate
Condition 5 2∶3 1∶3 1∶3 1∶3 1∶3 2∶3 1∶3
Condition 6 (NH 4) 2CO 3 Urea KOH NaOH NaHCO 3 Na 2CO 3 Ammoniacal liquor
Condition 7 99 80 70 60 50 85 75
Condition 8 5 12 15 24 20 18 10
Condition 9 4 3 5 4 3 2 1
Condition 10 200 180 120 150 100 80 60
Condition 11 40 48 22 72 30 10 60
Condition 12 / 1000 800 / 700 600 500
Condition 13 / 1 2 / 3 5 10
Condition 14 K N N K N Y Y
Condition 15 1000 300 330 800 350 480 440
Condition 16 0.8 3 2.5 2.5 1.5 2 0.5
The step condition of embodiment 22-28 is as shown in table 4, and remaining obtains not having the reunion stannic oxide nano material and being uniformly dispersed with embodiment 1 at last.
Table 4 is the step and the condition of the no reunion stannic oxide nano material of embodiment 22-28 preparation
Embodiment 22 23 24 25 26 27 28
Condition 1 150 1000 120 250 50 180 1200
Condition 2 a6 a1 i d e g a4
Condition 3 200 150 300 250 20 100 150
Condition 4 Nitrate Sulfate Chlorate Sulfate Chlorate Chlorate Nitrate
Condition 5 1∶2 1∶4 1∶4 1∶4 1∶4 1∶2 1∶4
Condition 6 HMT Urea NaOH KOH NaHCO 3 Na 2CO 3 Ammoniacal liquor
Condition 7 50 99 60 55 80 85 75
Condition 8 24 2 20 12 5 0.5 10
Condition 9 5 4 4 3 2 1 3
Condition 10 60 80 200 120 180 150 100
Condition 11 72 10 20 44 35 40 62
Condition 12 600 700 800 500 400 / 900
Condition 13 7 5 0.5 4 3 / 1
Condition 14 N N N Y Y K N
Condition 15 450 300 350 400 500 800 420
Condition 16 0.5 0.8 2.5 2 1.5 1 3
Step and the condition of embodiment 29-35 are as shown in table 5, and remaining obtains not having the reunion nanometer zirconium oxide and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion nanometer zirconium oxide of table 5. embodiment 29-35 preparation
Embodiment 29 30 31 32 33 34 35
Condition 1 50 100 200 1000 150 2000 20
Condition 2 a3 j k a4 e f i
Condition 3 150 50 300 250 30 100 200
Condition 4 Nitrate Sulfate Chlorate Acetate Sulfate Chlorate Nitrate
Condition 5 1∶2 1∶2 1∶2 1∶2 1∶2 1∶2 1∶2
Condition 6 NaOH Ammoniacal liquor NaOH KOH NaOH Ammoniacal liquor Ammoniacal liquor
Condition 7 55 65 75 80 90 99 60
Condition 8 20 24 5 2 1 12 15
Condition 9 4 3 2 1 5 4 5
Condition 10 60 150 120 100 80 200 180
Condition 11 72 20 10 48 60 50 35
Condition 12 600 700 800 500 400 / /
Condition 13 7 5 0.5 4 3 / /
Condition 14 N N A Y N K K
Condition 15 350 300 500 400 450 800 850
Condition 16 0.5 1 3 2 0.6 0.8 1.5
The step condition of embodiment 36-42 is as shown in table 6, and remaining obtains not having reunion monox nanometer material and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion monox nanometer material of table 6. embodiment 36-42 preparation
Embodiment 36 37 38 39 40 41 42
Condition 1 2 20 50 100 200 180 150
Condition 2 d e f a1 a2 c a3
Condition 3 150 150 300 250 30 100 200
Condition 4 Chlorate Chlorate Chlorate Chlorate Chlorate Chlorate Chlorate
Condition 5 / / / / / / /
Condition 6 / / / / / / /
Condition 7 55 60 99 85 95 75 65
Condition 8 5 8 1 24 2 20 12
Condition 9 3 4 5 4 1 2 3
Condition 10 200 80 180 160 150 120 60
Condition 11 10 25 12 48 35 45 72
Condition 12 100 500 600 700 800 900 /
Condition 13 12 7 5 4 3 1.5 /
Condition 14 N N Y Y N N K
Condition 15 400 320 500 440 390 460 1300
Condition 16 1.5 3 0.5 1.2 2 0.9 0.7
Step and the condition of embodiment 43-49 are as shown in table 7, and remaining obtains not having the reunion titanium dioxide nano material and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion titanium dioxide nano material of table 7. embodiment 43-49 preparation
Embodiment 43 44 45 46 47 48 49
Condition 1 2 20 50 100 200 180 150
Condition 2 d e i a1 a2 c a3
Condition 3 150 150 300 250 30 100 200
Condition 4 Sulfate Sulfate Chlorate Sulfate Chlorate Chlorate Chlorate
Condition 5 / / / / / / /
Condition 6 / / / / / / /
Condition 7 55 50 99 60 80 70 75
Condition 8 5 8 1 24 2 20 12
Condition 9 4 3 5 5 5 2 1
Condition 10 200 80 180 160 150 120 60
Condition 11 10 25 48 12 35 45 72
Condition 12 700 500 600 / 800 900 1000
Condition 13 7 12 5 / 3 1.5 0.5
Condition 14 A N A K N A A
Condition 15 400 350 500 900 390 460 370
Condition 16 1.5 3 0.5 2.5 2 0.9 0.7
Step and the condition of embodiment 50-56 are as shown in table 8, and remaining obtains not having reunion nitrogen adulterated TiOx and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion nitrogen adulterated TiOx of table 8. embodiment 50-56 preparation
Embodiment 50 51 52 53 54 55 56
Condition 1 2 20 50 100 200 180 150
Condition 2 m l k a1 a2 c a3
Condition 3 150 150 300 250 30 100 200
Condition 4 Chlorate Sulfate Chlorate Chlorate Chlorate Chlorate Sulfate
Condition 5 / / / / / / /
Condition 6 / / / / / / /
Condition 7 50 70 60 80 99 90 85
Condition 8 24 8 20 5 2 1 12
Condition 9 3 3 4 3 1 2 4
Condition 10 200 80 180 160 150 120 60
Condition 11 10 25 48 12 35 45 72
Condition 12 200 500 600 700 800 900 1300
Condition 13 12 7 5 4 3 1.5 0.5
Condition 14 N N N N N N N
Condition 15 400 350 500 440 320 450 420
Condition 16 1.5 3 0.5 1.2 2 0.9 0.7
Step and the condition of embodiment 57-63 are as shown in table 9, and remaining obtains not having the reunion aluminum-doped zinc oxide nanometer powder and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion aluminum-doped zinc oxide nanometer powder of table 9. embodiment 57-63 preparation
Embodiment 57 58 59 60 61 62 63
Condition 1 2000 1600 1200 800 500 100 20
Condition 2 d g f a1 a2 a3 c
Condition 3 150 10 100 200 250 50 300
Al∶Zn 1∶200 1∶100 1∶50 1∶60 1∶80 1∶90 1∶70
Condition 4 Nitrate Sulfate Chlorate Sulfate Nitrate Chlorate Nitrate
Condition 5 1∶2 1∶2 1∶2 1∶2 1∶1 1∶2 1∶1
Condition 6 NaOH KOH LiOH Ammoniacal liquor Na 2CO 3 Urea HMT
Condition 7 85 80 70 65 50 99 60
Condition 8 1 5 8 2 24 20 12
Condition 9 1 2 3 4 4 5 3
Condition 10 200 70 180 165 110 150 60
Condition 11 25 10 12 48 45 35 72
Condition 12 600 700 800 500 400 300 200
Condition 13 7 5 0.5 4 3 1.5 12
Condition 14 H A Y N 3H∶2Y 1N∶1H H
Condition 15 350 400 500 420 380 450 370
Condition 16 0.5 3 2.5 1.2 2 1.5 0.8
Note: Al: Zn is when the preparation aluminum-doped zinc oxide nanometer powder, the mol ratio of aluminium salt and zinc salt in the used slaine.Following examples together.
The step condition of embodiment 64-70 is as shown in table 10, and remaining obtains not having reunion ytterbium doped zinc oxide nano powder and being uniformly dispersed with embodiment 1 at last.
The step and the condition of the no reunion ytterbium doped zinc oxide nano powder of table 10. embodiment 64-70 preparation
Embodiment 64 65 66 67 68 69 70
Condition 1 200 180 150 100 20 2 50
Condition 2 e d a1 f a2 a3 c
Condition 3 150 150 300 250 30 100 200
Y∶Zn 1∶200 1∶100 1∶90 1∶150 1∶180 1∶120 1∶50
Condition 4 Nitrate Sulfate Chlorate Acetate Oxalates Zinc acetate Nitrate
Condition 5 1∶1 1∶2 1∶2 1∶2 1∶2 1∶2 1∶2
Condition 6 NaOH KOH LiOH NH 3 Na 2CO 3 Urea HMT
Condition 7 99 95 90 85 80 70 55
Condition 8 1 2 5 8 24 20 12
Condition 9 5 3 2 1 4 5 5
Condition 10 200 150 180 60 80 120 160
Condition 11 10 12 48 25 36 47 72
Condition 12 200 500 600 700 800 900 1300
Condition 13 5 3 12 4 7 0.5 1.5
Condition 14 H A Y N 3H∶2Y 1N∶1H H
Condition 15 350 400 440 500 370 460 390
Condition 16 1.5 3 0.6 2 1.2 0.8 0.5
The step condition of embodiment 71-77 is as shown in table 11, and remaining is with embodiment 1, obtains not having reunion Ga-doped zinc oxide nanocrystal at last and gives birth to and be uniformly dispersed.
The step and the condition of the no reunion Ga-doped zinc oxide nanocrystal of table 11. embodiment 71-77 preparation
Embodiment 71 72 73 74 75 76 77
Condition 1 1200 300 1400 500 100 20 2000
Condition 2 b e g f d c h
Condition 3 120 20 180 200 230 270 300
Ga∶Zn 1∶49 1∶55 1∶100 1∶200 1∶150 1∶80 1∶90
Condition 4 Nitrate Sulfate Chlorate Chlorate Acetate Sulfate Nitrate
Condition 5 1∶2 1∶2 1∶2 1∶2 1∶1 1∶1 1∶1
Condition 6 NaOH KOH Ammoniacal liquor LiOH Na 2CO 3 Urea (NH 4) 2CO 3
Condition 7 85 50 70 65 99 80 60
Condition 8 1 6 8 12 2 20 24
Condition 9 4 3 2 1 5 5 5
Condition 10 60 180 80 100 150 120 200
Condition 11 12 72 48 10 35 45 25
Condition 12 600 700 800 500 400 300 450
Condition 13 2 3 5 4 7 12 10
Condition 14 H H Y N 9H∶1Y 1N∶5H A
Condition 15 500 450 400 350 300 380 420
Condition 16 2 1.2 0.7 2.5 3 0.9 0.5
Step and the condition of embodiment 78-84 are as shown in table 12, and remaining is with embodiment 1, obtain not having reunion indium doped zinc oxide nano crystal at last and give birth to and be uniformly dispersed.
The step and the condition of the no reunion indium doped zinc oxide nano crystal of table 12. embodiment 78-84 preparation
Embodiment 78 79 80 81 82 83 84
Condition 1 20 300 1400 700 1000 500 2000
Condition 2 a2 i k e f c d
Condition 3 150 20 100 180 250 220 300
In∶Zn 1∶100 1∶60 1∶80 1∶90 1∶50 1∶200 1∶70
Condition 4 Nitrate Sulfate Chlorate Acetate Chlorate Sulfate Nitrate
Condition 5 1∶2 1∶2 1∶2 1∶2 1∶1 1∶2 1∶2
Condition 6 NaOH KOH LiOH NH 3 Na 2CO 3 Urea NH 4HCO 3
Condition 7 99 80 50 65 60 70 85
Condition 8 1 2 24 6 8 20 12
Condition 9 5 1 2 3 4 5 5
Condition 10 60 180 100 160 150 120 200
Condition 11 72 12 48 10 35 40 20
Condition 12 600 700 800 500 400 750 /
Condition 13 12 0.5 1.5 4 5 3 /
Condition 14 H H Y N N N K
Condition 15 370 350 500 440 380 450 800
Condition 16 3 2 0.8 1.2 1.5 1 0.5
Step and the condition of embodiment 85-91 are as shown in table 13, and remaining is with embodiment 1, obtain not having reunion tin-doped indium oxide nanocrystal at last and give birth to and be uniformly dispersed.
The step and the condition of the no reunion tin-doped indium oxide nanocrystal of table 13. embodiment 85-91 preparation
Embodiment 85 86 87 88 89 90 91
Condition 1 2000 20 1400 1000 1500 500 2000
Condition 2 a2 a4 a1 f e g a5
Condition 3 150 20 100 200 250 50 300
Sn∶In 1∶100 1∶50 1∶55 1∶60 1∶49 1∶57 1∶65
Condition 4 Nitrate Sulfate Chlorate Nitrate Sulfate Chlorate Chlorate
Condition 5 1∶3 1∶3 1∶3 1∶3 2∶3 1∶3 1∶3
Condition 6 NaOH KOH LiOH Ammoniacal liquor Na 2CO 3 Urea NaHCO 3
Condition 7 85 80 70 65 60 50 99
Condition 8 12 2 8 6 20 24 1
Condition 9 5 1 4 3 2 5 5
Condition 10 60 180 100 160 150 120 200
Condition 11 72 25 48 10 35 45 12
Condition 12 500 600 700 800 900 / /
Condition 13 7 5 3 1 0.5 / /
Condition 14 N N N A A K K
Condition 15 300 350 500 400 450 800 1300
Condition 16 2 3 0.7 1.2 1.5 0.9 0.5
Step and the condition of embodiment 92-98 are as shown in table 14, and remaining is with embodiment 1, obtain not having reunion antimony doped stannum oxide nano-crystal body at last and give birth to and be uniformly dispersed.
The step and the condition of the no reunion antimony doped stannum oxide nano-crystal body of table 14. embodiment 92-98 preparation
Embodiment 92 93 94 95 96 97 98
Condition 1 200 20 500 1000 1400 1600 2000
Condition 2 a8 a6 a7 k g i a3
Condition 3 120 20 150 220 240 270 300
Ab∶Sn 1∶100 1∶200 1∶55 1∶60 1∶50 1∶10 1∶5
Condition 4 Chlorate Sulfate Chlorate Chlorate Chlorate Chlorate Chlorate
Condition 5 1∶4 1∶4 1∶4 1∶4 1∶4 1∶4 1∶4
Condition 6 NaOH KOH NaOH Ammoniacal liquor NaOH Ammoniacal liquor Ammoniacal liquor
Condition 7 85 80 70 65 60 99 50
Condition 8 1 6 8 2 24 20 12
Condition 9 4 5 5 3 2 1 5
Condition 10 60 180 100 160 150 120 200
Condition 11 72 12 48 10 35 45 25
Condition 12 / / / 900 700 600 500
Condition 13 / / / 2 4 6 8
Condition 14 K K K N N N Y
Condition 15 900 800 700 500 400 350 350
Condition 16 2 3 5 1 3 2 4

Claims (2)

1. method that solves high-temperature calcination agglomeration of nano material is characterized in that step and condition are following:
1) macromolecule dispersing agent is dissolved in the water, concentration is 20-2000mg/mL; Described macromolecule dispersing agent is a solid polyethylene glycol; Polyvinyl alcohol; Polyacrylic acid; Carboxymethyl cellulose; Hydroxyethylcellulose; Polyvinylpyrrolidone; HPMA; Maleic acid-acrylic acid copolymer; Acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer; Acrylic acid-hydroxypropyl acrylate copolymer; Acrylic acid-acrylic acid ester-co-polymer of sulfonate; A kind of in acrylic acid-acrylic acid ester-phosphonic acids-sulfonate quadripolymer and the polyoxyethylated alkyl phenol formaldehyde condensation products;
Described solid polyethylene glycol is a kind of in polyethylene glycol-1000, polyethylene glycol-2000, polyethylene glycol-3000, polyethylene glycol-4000, polyethylene glycol-6000, polyethylene glycol-8000, cetomacrogol 1000 0 and the Macrogol 2000 0;
The solution temperature of described polyvinyl alcohol is 100 ℃; The solution temperature of other macromolecule dispersing agents is normal temperature;
2) the following salt that will prepare nano material of normal temperature is dissolved in the above-mentioned solution; Concentration is 10-300mg/mL; Be to stir 0.5-24h under 50-99 ℃ the condition in heating-up temperature; In the process of heated and stirred, add precipitating reagent by the stoichiometric proportion that generates the maximum deposition then, the deposition that obtains the precursor of nano material is dispersed among the solution of macromolecule dispersing agent; The salt of described preparation nano material is one or both in nitrate, sulfate, chlorate, acetate, oxalates, isopropoxide and the tartrate of zinc, aluminium, magnesium, indium, gallium, zirconium, tin or titanium; Described precipitating reagent is a kind of in NaOH, potassium hydroxide, lithium hydroxide, ammoniacal liquor, hexamethylenetetramine, urea, sodium acid carbonate, sodium carbonate, ammonium carbonate and the carbonic hydroammonium;
During synthesizing doped type binary composite oxide nano-material, two kinds of salt mol ratios of required preparation nano material are 1: 200-1: 5;
3) with step 2) the macromolecule dispersing agent solution of the presoma of the homodisperse nano material that obtains encloses in the bag filter; In secondary water, soaked 1-5 days; Remove residual ion; Put into drying box then in 60-200 ℃ of oven dry, the time is 10-72h, obtains the dry blends of the presoma and the macromolecule dispersing agent of nano material;
The presoma of the nano material that 4) step 3) is obtained and the dry blends of macromolecule dispersing agent; Under particular atmosphere, calcine 0.5-12h in 200-1300 ℃; Product after the calcining naturally cools to room temperature; Then it is inserted in the Muffle furnace in 300-500 ℃ of calcining 0.5-3h, remove macromolecule dispersing agent through oxygen-free atmosphere calcining back the coating in the nano-material surface generation, obtain not having the nano material of reunion; Described particular atmosphere is one or both in hydrogen, argon gas, ammonia and the nitrogen.
2. a kind of method that solves high-temperature calcination agglomeration of nano material as claimed in claim 1; It is characterized in that; Described step 4) is replaced with following steps: the presoma of the nano material that step 3) is obtained and the dry blends of macromolecule dispersing agent are inserted in the Muffle furnace in 300-1300 ℃ of calcining 0.5-12h, obtain not having the nano material of reunion.
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CN102689021A (en) * 2012-07-02 2012-09-26 昆明理工大学 Method for preparing micron spherical silver powder
US9394182B2 (en) 2012-07-12 2016-07-19 Akzo Nobel Chemicals International B.V. Free flowing salt composition prepared by evaporative crystallization
CN103233120B (en) * 2013-04-27 2016-01-20 湖南水口山有色金属集团有限公司 Improve flotation of silver concentrate surface-active method in oxygen pressure acidleach process
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WO2017066928A1 (en) * 2015-10-21 2017-04-27 深圳市广昌达石油添加剂有限公司 Multipurpose nano-mgo vanadium inhibitor, method for preparation and uses thereof
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CN115414933B (en) * 2022-09-30 2024-01-30 重庆市生态环境科学研究院 Noble metal supported catalyst and preparation method and application thereof

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