CN103496732A - Preparation method of high-conductivity aluminum-doped zinc oxide nano powder - Google Patents
Preparation method of high-conductivity aluminum-doped zinc oxide nano powder Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000000843 powder Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 27
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 25
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 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 claims abstract description 15
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004246 zinc acetate Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011787 zinc oxide Substances 0.000 claims description 41
- 235000012149 noodles Nutrition 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000001457 metallic cations Chemical class 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- -1 aluminum ions Chemical class 0.000 claims description 14
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 239000000047 product Substances 0.000 abstract description 13
- 239000002244 precipitate Substances 0.000 abstract 2
- 238000012369 In process control Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
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- 239000011259 mixed solution Substances 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 15
- 206010013786 Dry skin Diseases 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
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- 231100000252 nontoxic Toxicity 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of high-conductivity aluminum-doped zinc oxide nano powder. The preparation method comprises the steps of adding zinc acetate and aluminum nitrate which are taken as raw materials to a beaker, adding a mixed solution of ethylene glycol monomethyl ether and ethanol amine, and magnetically stirring to obtain uniform sol; drying the generated sol in an oven to obtain dry gel, and grinding the dry gel to obtain dry gel powder, namely a hydrothermal reaction precursor; adding the prepared hydrothermal reaction precursor to a hydrothermal kettle, and adding absolute ethyl alcohol as a solvent and NaOH as a mineralizing agent; sealing the reaction kettle, placing the reaction kettle in the oven at 120-180 DEG C, taking out a product after reaction, and filtering the product to obtain precipitate; washing and drying the precipitate to obtain the aluminum-doped zinc oxide powder. The preparation method prepares high-conductivity aluminum-doped zinc oxide nano powder at low temperature without a catalyst, and is simple in process control and synthesis-required instrument and is low in cost.
Description
Technical field
The present invention relates to the preparation method of aluminum-doped zinc oxide nanometer powder, particularly a kind of preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.
Background technology
Zinc oxide (ZnO) is a kind of N-shaped semi-conductor of broad-band gap.ZnO energy gap E at room temperature
g=3.37eV, be insulating material, thereby but by doping or because it does not strictly observe the existence that stoichiometric causes O room and Zn interstitial ion, so zinc oxide often shows good electroconductibility and the transparency.The Zinc oxide-base material is at the UV optical transmitting set, fluorescent material, and PZT (piezoelectric transducer), flat-panel monitor, solar cell, thermal control coating, the fields such as gas sensor have a wide range of applications.By elements such as doped with Al, Ga, In, the specific conductivity of ZnO can improve several orders of magnitude, is a kind of typical transparent conductive oxide (TCO) material.In these doped elements, due to Al doping ZnO (AZO) have cheap, nontoxic, to characteristics such as the high permeability of visible ray and high conductivity, having become the best materials that substitutes ITO (indium tin oxide) and become study hotspot, is a kind of TCO material that is hopeful commercial applications most.In addition, because the AZO powder has low resistance, it can be used as conductive filler material and adds in rubber, plastics, fiber and paper in case quiet and electromagnetic wave shielding.The AZO powder can adopt the conventional solid-state sintering process to make, but because high temperature can cause particle reunion bigger than normal and easy.Vapor phase process and direct current arc plasma also have been used to prepare the AZO nanometer powder, and still, these methods often relate to complicated technique and expensive equipment.In addition, various wet chemical methods, as adopt coprecipitation method, sol-gel method, soft chemical method etc. also successfully to synthesize the AZO nano-powder, but these methods still need to be at the temperature higher than 400 ℃ sintering, energy consumption is high and can cause the irregular and size distribution inequality of morphology microstructure, finally affects the performance of material.For example, the application for a patent for invention that application number is 201210111906.1 discloses the production method that a kind of sol-gel method prepares the AZO nano-powder, and its preparation temperature is just up to 700～800 ℃, and energy consumption is higher.Hydrothermal method/solvent-thermal method is a kind of important Low Temperature Wet chemistry method.Document " T.Strachowski, E.Grzanka, W.Lojkowski, A.Presz, M.Godlewski, S.Yatsunenko, H.Matysiak, R.R.Piticescu, and C.J.Monty, " Morphology and Luminescence Properties of Zinc Oxide Nanopowders Doped with Aluminum Ions Obtained by Hydrothermal and Vapor Condensation Methods, " Journal of Applied Physics, 102[7] 073513, (2007) " disclose a kind of 200 ℃ of methods of utilizing hydrothermal method to prepare the AZO powder, but existing, the powder of preparation reunites and the shortcoming such as pattern is uncontrollable.Document " S.P.Huang; Q.Xiao; H.Zhou; D.Wang, and W.J.Jiang, " Hydrothermal synthesis and conductive properties of Al-doped ZnO rod-like whiskers; " Journal of Alloys and Compounds, 486[1] L24-26 (2009) " a kind of method for preparing AZO whisker powder 160 ℃ of hydrothermal methods is disclosed, however the AZO obtained thus has higher resistivity (3.959 * 10
4Ω cm).The application for a patent for invention that publication number is CN100584716C discloses a kind of method for preparing the AZO nano-powder by solvent thermal reaction, but this AZO powder is only through obtaining high conductivity after 400～700 ℃ of sintering circuits in hydrogen atmosphere.
Summary of the invention
For the above-mentioned shortcoming and deficiency that overcomes prior art, the object of the present invention is to provide a kind of preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder, resistivity is low, and can under 120 ℃～180 ℃, synthesize, and saves the energy.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder comprises the following steps:
(1) take zinc acetate and aluminum nitrate as raw material, take zinc acetate and aluminum nitrate is put into beaker, wherein to account for the integral molar quantity of metallic cation (being comprised of zine ion and aluminum ion) be 0.5～5% to aluminum ions molar weight, the mixing solutions that adds again ethylene glycol monomethyl ether and thanomin, be made into uniform colloidal sol by magnetic agitation; In described colloidal sol, the volumetric molar concentration of metallic cation is 0.5～1.5mol/L;
(2) colloidal sol step (1) generated is put in baking oven, obtains xerogel after drying, and obtains dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor;
(3) the hydro-thermal reaction precursor prepared by step (2) is put into water heating kettle, and adds dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, and in described reaction soln, the concentration of NaOH is 0.3mol/L～2mol/L; Compactedness is 70%～80%;
(4) sealed reactor, be placed in reactor in the baking oven of 120 ℃～180 ℃, takes out the product in reactor after reacting 6～24h, is precipitated after filtration thing; Throw out use respectively deionized water and absolute ethanol washing clean, obtain high conductivity aluminium-doped zinc oxide powder after drying.
In the mixing solutions of the described ethylene glycol monomethyl ether of step (1) and thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 15～20.
In the described reaction soln of step (3), the concentration of NaOH is 1mol/L～2mol/L.
The time of the described magnetic agitation of step (1) is 1～3 hour.
The temperature of the described drying of step (2) is 80 ℃～90 ℃.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention has realized preparing high-conductivity aluminum-doping zinc oxide nanometer noodles powder under low temperature (120 ℃～180 ℃), the minimum 469 Ω cm that reach of resistivity.
(2) preparation method of the present invention, preparation temperature is 120～180 ℃, with existing preparation method, compares, temperature is low, has saved the energy.
(3) preparation method of the present invention, do not need catalyzer, and reaction product does not need to process through follow-up sintering, and technology controlling and process and synthetic required plant and instrument are simple, have further reduced production cost.
(4) preparation method of the present invention combines sol-gel technology and hydrothermal method, has fully demonstrated the advantage of the two.Raw material is prepared in liquid phase, and the even mixing on molecule/atomic level can accurately be controlled and realize to the content of each component, and the aluminum-doped zinc oxide nanometer powder of preparation has that pattern is controlled, doping is high and the advantage such as good dispersity.
(5) aluminum-doped zinc oxide nanometer powder that preparation method of the present invention obtains is nontoxic, reproducible, even particle size distribution, and pattern is controlled, complete crystallization.
The accompanying drawing explanation
The preparation flow figure of the AZO nano-powder that Fig. 1 is embodiments of the invention 1.
X ray diffraction (XRD) collection of illustrative plates of the AZO nano-powder that the aluminium doping that Fig. 2 is embodiments of the invention 1 preparation is 2.0mol%.
Scanning electron microscope (SEM) photo that Fig. 3 is the prepared aluminium doping of the embodiments of the invention 1 AZO nano-powder that is 2.0mol%.
Electron probe microanalyzer (EPMA) spectrogram that Fig. 4 is the prepared aluminium doping of the embodiments of the invention 1 AZO nano-powder that is 2.0mol%.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation method of the AZO nano-powder that as shown in Figure 1, the doping of the present embodiment is 2.0mol% comprises the following steps:
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 2%.Add the ethylene glycol monomethyl ether of 21ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 20 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 0.75mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 90 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.35mol/L, and compactedness is 80%.Sealed reactor, be placed in reactor in 120 ℃ of baking ovens, after reaction 12h, takes out the product in reactor, is precipitated after filtration thing; Throw out is respectively with within 12 hours, obtain a kind of aluminum-doped zinc oxide nanometer powder of high conductivity after deionized water and absolute ethanol washing 3 times at the baking oven inner drying of 85 ℃.The volume specific resistance of this powder is 469 Ω cm.
The x ray diffraction collection of illustrative plates that Fig. 2 is the prepared AZO nano-powder of the present embodiment.As shown in Figure 2, the pure phase AZO powder well-crystallized that prepared by the present embodiment.
The stereoscan photograph that Fig. 3 is the prepared AZO nano-powder of the present embodiment.As shown in Figure 2, aluminium-doped zinc oxide is nanometer rod.
Electron probe microanalyzer (EPMA) spectrogram that Fig. 4 is the prepared AZO nano-powder of the present embodiment.Except the C element (base material that C uses during from sample preparation), can only see the peak of Al, Zn, tri-kinds of elements of O in Fig. 4, and, from data analysis, element atomic ratio Al/ (Al+Zn) approaches 2%, this explanation aluminium has been incorporated in the lattice of zinc oxide.
For the preparation method with existing AZO is contrasted, the present embodiment can manage it following contrast experiment:
1, adopt traditional collosol and gel to prepare the AZO nano-powder that doping is 2.0mol%: dry gel powder prepared by the present embodiment is in air, 600 ℃ of lower sintering 2 hours, the AZO powder that to obtain doping after furnace cooling be 2.0mol%, the volume specific resistance that test obtains is 5.156 * 10
5Ω cm, the resistivity of the AZO powder prepared much larger than the present invention.
2, adopt traditional hydrothermal method to prepare the AZO nano-powder that doping is 2.0mol%: to adopt document (Journal of Alloys and Compounds, 486[1] L24-26 (2009)) disclosed hydrothermal method, take zinc nitrate (0.025mol) and aluminum nitrate and put into beaker, wherein to account for the integral molar quantity of metallic cation be 2% to aluminum ions molar weight, adds distilled water to dissolve the aqueous solution that obtains 60ml.Splash into again the NaOH of the 5mol/L of 60ml, mixing solutions is poured in water heating kettle after 1 hour by magnetic agitation, sealed reactor, and reactor is placed in 160 ℃ of baking ovens, take out the product in reactor after reaction 4h, be precipitated after filtration thing; Throw out obtains with the baking oven inner drying at 100 ℃ after deionized water and absolute ethanol washing 3 times the AZO nano-powder that doping is 2.0mol% in 12 hours respectively.The volume specific resistance that test obtains is 3.867 * 10
4Ω cm, the resistivity of the AZO powder also prepared much larger than the present invention.
In the reaction soln of the present embodiment, the concentration of NaOH is 0.35mol/L, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is spherical, and its volume specific resistance is 8499 Ω cm.
Embodiment 3
In the reaction soln of the present embodiment, the concentration of NaOH is 0.65mol/L, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph is presented in spherical nanoparticle and has occurred that some rhabdoliths, its volume specific resistance are 2304 Ω cm.
Embodiment 4
In the reaction soln of the present embodiment, the concentration of NaOH is 1mol/L, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph is presented in spherical nanoparticle and has occurred that more rhabdolith, its volume specific resistance are 1913 Ω cm.
Embodiment 5
In the reaction soln of the present embodiment, the concentration of NaOH is 1.65mol/L, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph is presented in the rod-like nano particle and has occurred that a small amount of crystal with irregular pattern, its volume specific resistance are 1367 Ω cm.
Embodiment 6
In the reaction soln of the present embodiment, the concentration of NaOH is 2mol/L, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph is presented in the rod-like nano particle and has occurred that a small amount of crystal with irregular pattern, its volume specific resistance are 1354 Ω cm.
Embodiment 7
The hydrothermal temperature of the present embodiment is 140 ℃, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 746 Ω cm.
Embodiment 8
The hydro-thermal reaction time of the present embodiment is 6 hours, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 521 Ω cm.
Embodiment 9
The hydro-thermal reaction time of the present embodiment is 16 hours, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 658 Ω cm.
Embodiment 10
The hydro-thermal reaction time of the present embodiment is 24 hours, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 732 Ω cm.
Embodiment 11
The hydrothermal temperature of the present embodiment is 160 ℃, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 848 Ω cm.
Embodiment 12
The hydrothermal temperature of the present embodiment is 180 ℃, and remaining condition and step are identical with embodiment 1, obtain a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder.Stereoscan photograph shows that this nano-powder is bar-shaped, and its volume specific resistance is 1109 Ω cm.
Embodiment 13
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 0.5%.Add the ethylene glycol monomethyl ether of 21ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 16 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 0.5mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 80 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, obtain reaction soln, in reaction soln, the concentration of NaOH is 0.66mol/L, and compactedness is 80%.Sealed reactor, be placed in reactor in 120 ℃ of baking ovens, after reaction 12h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 85 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 4633 Ω cm.
Embodiment 14
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 1%.Add the ethylene glycol monomethyl ether of 25ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 18 again, by magnetic agitation 3 hours, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 0.65mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 90 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.35mol/L, and compactedness is 70%.Sealed reactor, be placed in reactor in 140 ℃ of baking ovens, after reaction 16h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 85 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 3058 Ω cm.
Embodiment 15
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 1.5%.Add the ethylene glycol monomethyl ether of 21ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 20 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 0.85mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 90 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1mol/L; Compactedness is 75%.Sealed reactor, be placed in reactor in 120 ℃ of baking ovens, after reaction 12h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 90 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 2304 Ω cm.
Embodiment 16
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 2.5%.Add the ethylene glycol monomethyl ether of 25ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 18 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 1mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 85 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.35mol/L, and compactedness is 70%.Sealed reactor, be placed in reactor in 120 ℃ of baking ovens, after reaction 16h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 90 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 3328 Ω cm.
Embodiment 17
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 3%.Add the ethylene glycol monomethyl ether of 30ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 16 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 1.2mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 90 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.5mol/L, and compactedness is 80%.Sealed reactor, be placed in reactor in 120 ℃ of baking ovens, after reaction 16h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 90 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 3504 Ω cm.
Embodiment 18
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 3.5%.Add the ethylene glycol monomethyl ether of 25ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 18 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 1.2mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 85 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.65mol/L, and compactedness is 75%.Sealed reactor, be placed in reactor in 140 ℃ of baking ovens, after reaction 16h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 90 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 3728 Ω cm.
Embodiment 19
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 4%.Add the ethylene glycol monomethyl ether of 30ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 20 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 1.4mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 85 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer, in reaction soln, the concentration of NaOH is 1.8mol/L, and compactedness is 70%.Sealed reactor, be placed in reactor in 140 ℃ of baking ovens, after reaction 20h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 16 hours with the baking oven inner drying at 85 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 4051 Ω cm.
Take zinc acetate and aluminum nitrate is put into beaker, the integral molar quantity that wherein aluminum ions molar weight accounts for metallic cation is 5%.Add the ethylene glycol monomethyl ether of 30ml and the mixing solutions of thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 20 again, by magnetic agitation 1 hour, is made into uniform colloidal sol, and in colloidal sol, the volumetric molar concentration of metallic cation is 1.5mol/L.The colloidal sol of generation is put in baking oven, obtains xerogel after 85 ℃ of dryings, and obtain dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor; The hydro-thermal reaction precursor of preparation is put into to water heating kettle, and add dehydrated alcohol as solvent, obtain reaction soln, in reaction soln, the concentration of NaOH is 2mol/L, and compactedness is 80%.Sealed reactor, be placed in reactor in 180 ℃ of baking ovens, after reaction 12h, takes out the product in reactor, is precipitated after filtration thing; Throw out obtains a kind of high-conductivity aluminum-doping zinc oxide nanometer noodles powder in 12 hours with the baking oven inner drying at 90 ℃ after deionized water and absolute ethanol washing 3 times respectively.The volume specific resistance of this powder is 4239 Ω cm.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (5)
1. the preparation method of a high-conductivity aluminum-doping zinc oxide nanometer noodles powder, is characterized in that, comprises the following steps:
(1) take zinc acetate and aluminum nitrate as raw material, take zinc acetate and aluminum nitrate is put into beaker, wherein to account for the integral molar quantity of metallic cation be 0.5～5% to aluminum ions molar weight, then add the mixing solutions of ethylene glycol monomethyl ether and thanomin, by magnetic agitation, is made into uniform colloidal sol; In described colloidal sol, the volumetric molar concentration of metallic cation is 0.5～1.5mol/L;
(2) colloidal sol step (1) generated is put in baking oven, obtains xerogel after drying, and obtains dry gel powder through grinding, be i.e. the hydro-thermal reaction precursor;
(3) the hydro-thermal reaction precursor prepared by step (2) is put into water heating kettle, and adds dehydrated alcohol as solvent, and NaOH obtains reaction soln as mineralizer; In described reaction soln, the concentration of NaOH is 0.3mol/L～2mol/L; Compactedness is 70%～80%;
(4) sealed reactor, be placed in reactor in the baking oven of 120 ℃～180 ℃, takes out the product in reactor after reacting 6～24h, is precipitated after filtration thing; Throw out use respectively deionized water and absolute ethanol washing clean, obtain high conductivity aluminium-doped zinc oxide powder after drying.
2. the preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder according to claim 1, is characterized in that, in the mixing solutions of the described ethylene glycol monomethyl ether of step (1) and thanomin, the volume ratio of ethylene glycol monomethyl ether and ethanolamine solutions is 15～20.
3. the preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder according to claim 1, is characterized in that, in the described reaction soln of step (3), the concentration of NaOH is 1.0mol/L～2mol/L.
4. the preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder according to claim 1, is characterized in that, the time of the described magnetic agitation of step (1) is 1～3 hour.
5. the preparation method of high-conductivity aluminum-doping zinc oxide nanometer noodles powder according to claim 1, is characterized in that, the temperature of the described drying of step (2) is 80 ℃～90 ℃.
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